Advanced Quantum Physics

Ben Simons
Contents

1 Wave mechanics and the Schrödinger equation 1

1.1 Historical foundations of quantum physics . . . . . . . . . . . . 1
1.1.1 Black-body radiation . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Photoelectric effect . . . . . . . . . . . . . . . . . . . . . 3
1.1.3 Compton Scattering . . . . . . . . . . . . . . . . . . . . 3
1.1.4 Atomic spectra . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Wave mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.1 Maxwell’s wave equation . . . . . . . . . . . . . . . . . . 6
1.2.2 Schrödinger’s equation . . . . . . . . . . . . . . . . . . . 8
1.2.3 Time-independent Schrödinger equation . . . . . . . . . 8
1.2.4 Particle flux and conservation of probability . . . . . . . 9

2 Quantum mechanics in one dimension 10

2.1 Wave mechanics of unbound particles . . . . . . . . . . . . . . 10
2.1.1 Free particle . . . . . . . . . . . . . . . . . . . . . . . . 10
2.1.2 Potential step . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.3 Potential barrier . . . . . . . . . . . . . . . . . . . . . . 13
2.1.4 The rectangular potential well . . . . . . . . . . . . . . 15
2.2 Wave mechanics of bound particles . . . . . . . . . . . . . . . . 15
2.2.1 The rectangular potential well (continued) . . . . . . . . 15
2.2.2 The δ-function potential well . . . . . . . . . . . . . . . 16
2.2.3 Info: The δ-function model of a crystal . . . . . . . . . 17

3 Operator methods in quantum mechanics 19

3.1 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.1.1 Time-evolution operator . . . . . . . . . . . . . . . . . . 21
3.1.2 Uncertainty principle for non-commuting operators . . . 22
3.1.3 Time-evolution of expectation values . . . . . . . . . . . 23
3.2 Symmetry in quantum mechanics . . . . . . . . . . . . . . . . . 24
3.2.1 Observables as generators of transformations . . . . . . 24
3.2.2 Consequences of symmetries: multiplets . . . . . . . . . 26
3.3 The Heisenberg Picture . . . . . . . . . . . . . . . . . . . . . . 27
3.4 Quantum harmonic oscillator . . . . . . . . . . . . . . . . . . . 27
3.5 Postulates of quantum theory . . . . . . . . . . . . . . . . . . . 31

4 Quantum mechanics in more than one-dimension 33

4.1 Rigid diatomic molecule . . . . . . . . . . . . . . . . . . . . . . 33
4.2 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . 34
4.2.1 Commutation relations . . . . . . . . . . . . . . . . . . . 34
4.2.2 Eigenvalues of angular momentum . . . . . . . . . . . . 34
4.2.3 Representation of the angular momentum states . . . . 36
4.3 The central potential . . . . . . . . . . . . . . . . . . . . . . . . 38
4.4 Atomic hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . 39

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CONTENTS vi

5 Motion in a magnetic field 44

5.1 Classical mechanics of a particle in a field . . . . . . . . . . . . 44
5.2 Quantum mechanics of a particle in a field . . . . . . . . . . . . 46
5.3 Atomic hydrogen: Normal Zeeman effect . . . . . . . . . . . . . 47
5.4 Gauge invariance and the Aharonov-Bohm effect . . . . . . . . 48
5.5 Free electrons in a magnetic field: Landau levels . . . . . . . . 50

6 Spin 53
6.1 Spinors, spin pperators, Pauli matrices . . . . . . . . . . . . . . 54
6.2 Relating the spinor to the spin direction . . . . . . . . . . . . . 55
6.3 Spin precession in a magnetic field . . . . . . . . . . . . . . . . 56
6.3.1 Paramagnetic Resonance . . . . . . . . . . . . . . . . . 56
6.4 Addition of angular momenta . . . . . . . . . . . . . . . . . . . 58
6.4.1 Addition of two spin 1/2 degrees of freedom . . . . . . . 59
6.4.2 Addition of angular momentum and spin . . . . . . . . 60
6.4.3 Addition of two angular momenta J = 1 . . . . . . . . . 61

7 Approximation methods for stationary states 62

7.1 Time-independent perturbation theory . . . . . . . . . . . . . . 62
7.1.1 The Perturbation Series . . . . . . . . . . . . . . . . . . 63
7.1.2 First order perturbation theory . . . . . . . . . . . . . . 64
7.1.3 Second order perturbation theory . . . . . . . . . . . . . 65
7.2 Degenerate perturbation theory . . . . . . . . . . . . . . . . . . 67
7.3 Variational method . . . . . . . . . . . . . . . . . . . . . . . . . 69
7.4 Wentzel, Kramers and Brillouin (WKB) method . . . . . . . . 72
7.4.1 Semi-classical approximation to leading order . . . . . . 73
7.4.2 Next to leading order correction . . . . . . . . . . . . . 74
7.4.3 Connection formulae, boundary conditions and quanti-
zation rules . . . . . . . . . . . . . . . . . . . . . . . . . 75

8 Identical Particles 78
8.1 Quantum statistics . . . . . . . . . . . . . . . . . . . . . . . . . 78
8.2 Space and spin wavefunctions . . . . . . . . . . . . . . . . . . . 80
8.3 Physical consequences of particle statistics . . . . . . . . . . . . 81
8.4 Ideal quantum gases . . . . . . . . . . . . . . . . . . . . . . . . 83
8.4.1 Non-interacting Fermi gas . . . . . . . . . . . . . . . . . 84
8.4.2 Ideal Bose gas . . . . . . . . . . . . . . . . . . . . . . . 86

9 Atomic structure 89
9.1 The “real” hydrogen atom . . . . . . . . . . . . . . . . . . . . . 90
9.1.1 Relativistic correction to the kinetic energy . . . . . . . 90
9.1.2 Spin-orbit coupling . . . . . . . . . . . . . . . . . . . . . 91
9.1.3 Darwin term . . . . . . . . . . . . . . . . . . . . . . . . 93
9.1.4 Lamb shift . . . . . . . . . . . . . . . . . . . . . . . . . 93
9.1.5 Hyperfine structure . . . . . . . . . . . . . . . . . . . . . 95
9.2 Multi-electron atoms . . . . . . . . . . . . . . . . . . . . . . . . 96
9.2.1 Central field approximation . . . . . . . . . . . . . . . . 97
9.3 Coupling schemes . . . . . . . . . . . . . . . . . . . . . . . . . . 102
9.3.1 LS coupling scheme . . . . . . . . . . . . . . . . . . . . 102
9.3.2 jj coupling scheme . . . . . . . . . . . . . . . . . . . . . 105
9.4 Atomic spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
9.4.1 Single electron atoms . . . . . . . . . . . . . . . . . . . 107
9.4.2 Helium and alkali earths . . . . . . . . . . . . . . . . . . 108
9.4.3 Multi-electron atoms . . . . . . . . . . . . . . . . . . . . 109

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CONTENTS vii

9.5 Zeeman effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

9.5.1 Single-electron atoms . . . . . . . . . . . . . . . . . . . 109
9.5.2 Multi-electron atoms . . . . . . . . . . . . . . . . . . . . 110

10 From molecules to solids 112

10.1 The H+2 ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
10.2 The H2 Molecule . . . . . . . . . . . . . . . . . . . . . . . . . . 116
10.3 From molecules to solids . . . . . . . . . . . . . . . . . . . . . . 118
10.4 Molecular spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 122
10.4.1 Molecular rotation . . . . . . . . . . . . . . . . . . . . . 124
10.4.2 Vibrational transitions . . . . . . . . . . . . . . . . . . . 125

11 Field theory: from phonons to photons 127

11.1 Quantization of the classical atomic chain . . . . . . . . . . . . 127
11.1.1 Classical chain . . . . . . . . . . . . . . . . . . . . . . . 127
11.1.2 Quantum chain . . . . . . . . . . . . . . . . . . . . . . . 130
11.2 Quantum electrodynamics . . . . . . . . . . . . . . . . . . . . . 134
11.2.1 Classical theory of the electromagnetic field . . . . . . . 134
11.2.2 Quantum field theory of the electromagnetic field . . . . 137

12 Time-dependent perturbation theory 139

12.1 Time-dependent potentials: general formalism . . . . . . . . . . 139
12.2 Time-dependent perturbation theory . . . . . . . . . . . . . . . 141
12.3 “Sudden” perturbation . . . . . . . . . . . . . . . . . . . . . . . 143
12.3.1 Harmonic perturbations: Fermi’s Golden Rule . . . . . 143
12.3.2 Info: Harmonic perturbations: second-order transitions 144

13 Radiative transitions 146

13.1 Coupling of matter to the electromagnetic field . . . . . . . . . 146
13.1.1 Spontaneous emission . . . . . . . . . . . . . . . . . . . 147
13.1.2 Absorption and stimulated emission . . . . . . . . . . . 148
13.2 Selection Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
13.3 Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
13.3.1 Operating principles of a laser . . . . . . . . . . . . . . 153
13.3.2 Gain mechanism . . . . . . . . . . . . . . . . . . . . . . 153
13.4 Driven harmonic oscillator . . . . . . . . . . . . . . . . . . . . . 155

14 Scattering theory 157

14.1 Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
14.2 Method of partial waves . . . . . . . . . . . . . . . . . . . . . . 160
14.3 The Born approximation . . . . . . . . . . . . . . . . . . . . . . 162
14.4 Info: Scattering of identical particles . . . . . . . . . . . . . . 164
14.5 Scattering by an atomic lattice . . . . . . . . . . . . . . . . . . 165

15 Relativistic Quantum Mechanics 167

15.1 Klein-Gordon equation . . . . . . . . . . . . . . . . . . . . . . . 170
15.2 Dirac Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
15.2.1 Density and Current . . . . . . . . . . . . . . . . . . . . 174
15.2.2 Relativistic Covariance . . . . . . . . . . . . . . . . . . . 174
15.2.3 Angular momentum and spin . . . . . . . . . . . . . . . 175
15.2.4 Parity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
15.3 Free Particle Solution of the Dirac Equation . . . . . . . . . . . 176
15.3.1 Klein paradox: anti-particles . . . . . . . . . . . . . . . 177
15.4 Quantization of relativistic fields . . . . . . . . . . . . . . . . . 180

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15.4.1 Info: Scalar field: Klein-Gordon equation revisited . . 180

15.4.2 Info: Charged Scalar Field . . . . . . . . . . . . . . . . 182
15.4.3 Info: Dirac Field . . . . . . . . . . . . . . . . . . . . . 183
15.5 The low energy limit of the Dirac equation . . . . . . . . . . . 184

16 Problem sets 187

16.1 Problem Set I . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
16.2 Problem Set II . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
16.3 Problem Set III . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
16.4 Problem Set IV . . . . . . . . . . . . . . . . . . . . . . . . . . . 216

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Preface
Quantum mechanics underpins a variety of broad subject areas within physics
and the physical sciences from high energy particle physics, solid state and
atomic physics through to chemistry. As such, the subject resides at the core
of every physics programme. By building upon the conceptual foundations
introduced in the IB Quantum Physics course, the aim of Part II Advanced
Quantum Physics is to develop further conceptual insights and technical flu-
ency in the subject.
Although 24 lectures is a long course to prepare(!), it is still insufficient
to cover all of the topics that different physicists will describe as “core”. For
example, some will argue that concepts of quantum computation should al-
ready be included as an established component of the core. Simiilarly, in the
field of quantum optics, some will say that a detailed knowledge of atomic and
molecular spectroscopy is key. In the field of solid state physics, the concept
of second quantization in many-body physics is also considered central. In all
of these cases, we will be able to touch only the surface of the subject. How-
ever, the material included in this course has been chosen to cover the key
conceptual foundations that provide access to these more advanced subjects,
the majority of which will be covered in subequent optional courses in Part II
and Part III.
In the following, we list an approximate “lecture by lecture” synopsis of
the different topics treated in this course. Those topics marked by a † will be
covered if time permits.
1 Foundations of quantum physics: Overview of course structure and
organization; brief revision of historical background: from wave mechan-
ics to the Schrödinger equation.
2 Quantum mechanics in one dimension: Wave mechanics of un-
bound particles; potential step; potential barrier and quantum tunnel-
ing; bound states; rectangular well; δ-function potential well; † Kronig-
Penney model of a crystal.
3 Operator methods in quantum mechanics: Operator methods;
uncertainty principle for non-commuting operators; Ehrenfest theorem
and the time-dependence of operators; symmetry in quantum mechan-
ics; Heisenberg representation; postulates of quantum theory; quantum
harmonic oscillator.
4 Quantum mechanics in more than one dimension: Rigid diatomic
molecule; angular momentum; commutation relations; raising and low-
ering operators; representation of angular momentum states.
5 Quantum mechanics in more than one dimension: Central po-
tential; atomic hydrogen; radial wavefunction.
6 Motion of charged particle in an electromagnetic field: Classical
mechanics of a particle in a field; quantum mechanics of particle in a
field; atomic hydrogen – normal Zeeman effect; † diamagnetic hydrogen
and quantum chaos; gauge invariance and the Aharonov-Bohm effect;
free electrons in a magnetic field – Landau levels.
7-8 Quantum mechanical spin: History and the Stern-Gerlach experi-
ment; spinors, spin operators and Pauli matrices; relating the spinor to
spin direction; spin precession in a magnetic field; parametric resonance;
addition of angular momenta.

Advanced Quantum Physics

 ii

9 Time-independent perturbation theory: Perturbation series; first

and second order expansion; degenerate perturbation theory; Stark ef-
fect; nearly free electron model.

10 Variational and † WKB method: Ground state energy and eigenfunc-

tions; application to helium; excited states; † Wentzel-Kramers-Brillouin
method.

11 Identical particles: Particle indistinguishability and quantum statis-

tics; space and spin wavefunctions; consequences of particle statistics;
ideal quantum gases; degeneracy pressure in neutron stars; Bose-Einstein
condensation in ultracold atomic gases.

12-13 Atomic structure: Relativistic corrections; spin-orbit coupling; Dar-

win structure; Lamb shift; hyperfine structure; Multi-electron atoms;
Helium; Hartree approximation and beyond; Hund’s rule; periodic ta-
ble; coupling schemes LS and jj; atomic spectra; Zeeman effect.

14-15 Molecular structure: Born-Oppenheimer approximation; H2 +ion; H2

molecule; ionic and covalent bonding; molecular spectra; rotation; nu-
clear statistics; vibrational transitions.

16 Field theory of atomic chain: From particles to fields: classical field

theory of the harmonic atomic chain; quantization of the atomic chain;
phonons.

17 Quantum electrodynamics: Classical theory of the electromagnetic

field; theory of waveguide; quantization of the electromagnetic field and
photons.

18 Time-independent perturbation theory: Time-evolution operator;

Rabi oscillations in two level systems; time-dependent potentials – gen-
eral formalism; perturbation theory; sudden approximation; harmonic
perturbations and Fermi’s Golden rule; second order transitions.

19 Radiative transitions: Light-matter interaction; spontaneous emis-

sion; absorption and stimulated emission; Einstein’s A and B coefficents;
dipole approximation; selection rules; lasers.

20-21 Scattering theory I: Basics; elastic and inelastic scattering; method

of particle waves; Born approximation; scattering of identical particles.

22-24 Relativistic quantum mechanics: History; Klein-Gordon equation;

Dirac equation; relativistic covariance and spin; free relativistic particles
and the Klein paradox; antiparticles and the positron; Coupling to EM
field: gauge invariance, minimal coupling and the connection to non-
relativistic quantum mechanics; † field quantization.

Handout
To accompany the course, a substantial handout has been prepared.1 In some
cases, the handout contains material (usually listed as Info blocks) that goes
beyond the scope of the lectures. Needless to say, the examination will be
1
I should note that, in preparing the handout, I have made use of some web-based material
– particularly the excellent lecture notes by Fowler at Virginia – and notes prepared by David
Ward in previous generations of the course. I have also included links to useful material on
the course webpage.

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 iii

limited to material that is covered in lectures and not the handout. Since
this handout is substantially new, it is inevitable that there will be some
typographical errors – some of them may even be important... I would be
most grateful if you could e-mail the errors that you find to bds10@cam. I will
try to maintain a “corrected” set of notes on the web.
The overheads used in lectures can also be recovered from the course web-
site along with other relevant and useful material.
2

Problem Sets
The problem sets are a vital and integral part of the course providing the means
to reinforce key ideas as well as practice techniques. Problems indicated by a †
symbol are regarded as challenging. Throughout these notes, I have included
a number of simpler exercises which may be completed “along the way”, and
aim to reinforce some of the ideas developed in the text.

Books
As a core of every undergraduate and graduate physics programme, there is
a wealth of excellent textbooks on the subject. Choosing ones that suit is a
subjective exercise. Apart from the handout, I am not aware of a text that
addresses all of the material covered in this course: Most are of course more
dense and far-reaching, and others are simply more advanced or imbalanced
towards specialist topics. At the same time, I would not recommend relying
solely on the handout. Apart from the range of additional examples they offer,
the textbooks will often provide a more erudite and engaging discussion of the
material. Although there are too many texts on the subject to discuss every
one, I have included below some of the books that I believe to be particularly
useful.

2
http://www.tcm.phy.cam.ac.uk/~bds10/aqp.html

Advanced Quantum Physics

Bibliography

[1] B. H. Bransden and C. J. Joachain, Quantum Mechanics, (2nd edition, Pear-

son, 2000). This is a classic text which covers core elements of advanced quantum
mechanics. It is particularly strong in the area of atomic physics, but weaker on
many-particle physics.
[2] S. Gasiorowicz, Quantum Physics, (2nd edn. Wiley 1996, 3rd edition, Wiley,
2003). This is an excellent textbook that covers material at approximately the right
level for the course. However, the published text (as opposed to the supplementary
material available online) omits some topics which are addressed in this course.
[3] H. Haken and H. C. Wolf, The Physics of Atoms and Quanta, (6th edn
Springer, 2000). This is a more advanced text which addresses many aspects of
atomic physics and quantum optics in a readable manner.
[4] K. Konishi and G. Paffuti, Quantum Mechanics: A New Introduction,
(OUP, 2009). This is a new text which includes some entertaining new topics within
an old field. It also has a useful set of mathematica-based examples if you can get
hold of the disk!
[5] L. D. Landau and L. M. Lifshitz, Quantum Mechanics: Non-Relativistic
Theory, Volume 3, (Butterworth-Heinemann, 3rd edition, 1981). This is a rich
and classic text which covers the many of the core topics in this course in most cases
at a level that goes well-beyond our target.
[6] F. Schwabl, Quantum Mechanics, (Springer, 4th edition, 2007). This book
provides a clear exposition of the core topics addressed at the same level as the
current text.
[7] R. Shankar, Principles of Quantum Mechanics, (Springer; 2nd edition,
1994). This is a very interesting and idiosyncratic text that I particularly like. It
is not comprehensive enough to cover every topic in this course. But where there is
overlap, it provides an excellent and interesting commentary.

Advanced Quantum Physics

Chapter 1

Wave mechanics and the

Schrödinger equation
William Thomson, 1st Baron
Kelvin 1824-1907
Kelvin was ed-
ucated at Glas-
Although this lecture course will assume a familiarity with the basic concepts gow and Cam-
of wave mechanics, to introduce more advanced topics in quantum theory, it bridge. He be-
came professor of
makes sense to begin with a concise review of the foundations of the subject. natural philoso-
In particular, in the first chapter of the course, we will begin with a brief phy at Glasgow in
1846. From 1846
discussion of the historical challenges that led to the development of quantum to 1851 Kelvin
theory almost a century ago. edited the “Cambridge and Dublin
The formulation of a consistent theory of statistical mechanics, electrody- Mathematical Journal,” to which he
contributed several important papers.
namics and special relativity during the latter half of the 19th century and Some of his chief discoveries are an-
the early part of the 20th century had been a triumph of “unification”. How- nounced in the “Secular Coating of
the Earth,” and the Bakerian lec-
ever, the undoubted success of these theories gave an impression that physics ture, the “Electrodynamic Qualities
was a mature, complete, and predictive science. Nowehere was confidence of Metals.” He invented the quad-
rant, portable, and absolute elec-
expressed more clearly than in the famous quote made at the time by Lord trometers, and other scientific instru-
Kelvin: There is nothing new to be discovered in physics now. All that re- ments. In January 1892, he was
mains is more and more precise measurement. However, there were a number raised to the peerage as Lord Kelvin.

of seemingly unrelated and unsettling problems that challenged the prevailing

Gustav Robert Kirchhoff 1824-
theories. 1887
A German
physicist who
1.1 Historical foundations of quantum physics contributed
the fundamental
to

understanding of
1.1.1 Black-body radiation electrical circuits,
spectroscopy,
In 1860, Gustav Kirchhoff introduced the concept of a “black body”, an ob- and the emission
of black-body
ject that absorbs all electromagnetic radiation that falls upon it – none passes radiation by heated objects. He
through and none is reflected. Since no light is reflected or transmitted, the coined the term “black body”
object appears black when it is cold. However, above absolute zero, a black radiation in 1862, and two sets of
independent concepts in both circuit
body emits thermal radiation with a spectrum that depends on temperature. theory and thermal emission are
To determine the spectrum of radiated energy, it is helpful to think of a black named “Kirchhoff’s laws” after him.
body as a thermal cavity at a temperature, T . The energy radiated by the cav-
ity can be estimated by considering the resonant modes. In three-dimensions, John William Strutt, 3rd Baron
the number of modes, per unit frequency per unit volume is given by Rayleigh OM (1842-1919)
An English physi-
cist who, with
8πν 2
N (ν)dν = 3 dν , William Ramsay,
discovered the el-
c
ement argon, an
where, as usual, c is the speed of light.1 achievement for
which he earned
1 the Nobel Prize
If we take the cavity to have dimension L3 , the modes of the cavity involve wave numbers in 1904. He also
k = πn/L where n = (nx , ny , nz ) denote the vector of integers nx = 0, 1, 2, · · · ∞, etc. The discovered the
corresponding frequency of each mode is given by ν = c|k|/2π, where c is the velocity of phenomenon of Rayleigh scattering,
light. The number of modes (per unit volume) having frequencies between ν and ν + dν is explaining why the sky is blue, and
predicted the existence of surface
waves known as Rayleigh waves.
Advanced Quantum Physics
1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 2

Figure 1.1: The COBE (Cos-

mic Background Explorer) satel-
lite made careful measurements
of the shape of the spec-
trum of the emission from
the cosmic microwave back-
ground. As one can see, the be-
haviour at low-frequencies (long-
wavelengths) conforms well with
the predicted Rayleigh-Jeans
law translating to a temper-
ature of 2.728K. However, at
high frequencies, there is a de-
parture from the predicted ν 2
dependence.

The amount of radiation emitted in a given frequency range should be Max Karl Ernst Ludwig Planck
proportional to the number of modes in that range. Within the framework 1858-1947
German physicist
of classical statistical mechanics, each of these modes have an equal chance whose work
of being excited, and the average energy in each mode is kB T (equipartition), provided the
bridge between
where kB is the Boltzmann constant. The corresponding energy density is classical and
therefore given by the Rayleigh-Jeans law, modern physics.
Around 1900
Planck developed
8πν 2
ρ(ν, T ) = kB T . a theory explain
c3 the nature of
black-body radiation. He proposed
This result predicts that ρ(ν, T ) increases without bound at high frequencies, that energy is emitted and absorbed
in discrete packets or “quanta,”
ν — the untraviolet (UV) catastrophe. However, such behaviour stood in and that these had a definite size –
contradiction with experiment which revealed that the short-wavelength de- Planck’s constant. Planck’s finding
didn’t get much attention until the
pendence was quite benign (see, e.g., Fig. 1.1). idea was furthered by Albert Einstein
To resolve difficulties presented by the UV catastrophe, Planck hypothe- in 1905 and Niels Bohr in 1913.
sized that, for each mode ν, energy is quantized in units of hν, where h denotes Planck won the Nobel Prize in 1918,
and, together with Einstein’s theory
the Planck constant. In this case, the energy of each mode is given by2 of relativity, his quantum theory
changed the field of physics.
!∞ −nhν/kB T
n=0 nhνe hν
!ε(ν)" = ! ∞ = hν/k T ,
n=0 e−nhν/kB T e B −1

leading to the anticipated suppression of high frequency modes. From this

result one obtains the celebrated Planck radiation formula,
Albert Einstein 1879-1955
was a German-
8πν 2 8πhν 3 1 born theoretical
ρ(ν, T ) = !ε(ν)" = . (1.1)
c3 c3 ehν/kB T − 1 physicist. He is
best known for
his theory of rela-
This result conforms with experiment (Fig. 1.1), and converges on the Rayleigh- tivity and specifi-
Jeans law at low frequencies, hν/kB T → 0. cally mass-energy
equivalence, ex-
Planck’s result suggests that electromagnetic energy is quantized: light of pressed by the
wavelength λ = c/ν is made up of quanta each of which has energy hν. The equation E =
mc2 . Einstein received the 1921 No-
equipartion law fails for oscillation modes with high frequencies, hν % kB T . A bel Prize in Physics “for his services
2
to Theoretical Physics, and especially
therefore given by N (ν)dν = L13 × 2 × 18 × (4πk )dk
(π/L)3
, where the factor of 2 accounts for the two for his discovery of the law of the pho-
2 toelectric effect.”
polarizations, the factor (4πk )dk is the volume of the shell from k to k + dk in reciprocal
space, the factor of 1/8 accounts for the fact that only positive wavenumbers are involved in
the closed cavity, and the factor of (π/L)3 denotes the volume of phase space occupied by
each mode. Rearranging the equation, and noting that dk = 2πdν/c, we obtain the relation
in the text.
2 P∞ −βnhν
If we define the partition function, Z = n=0 e , where β = 1/kBP T , #E$ =
∞ n
−∂β ln Z. Making use of the formula for the sum of a geometric progression, n=0 r =
1/(1 − r), we obtain the relation.

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1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 3

Figure 1.2: Measurements of

the photoelectric effect taken
by Robert Millikan showing the
variation of the stopping voltage,
eV , with variation of the fre-
quency of incident light. Figure
reproduced from Robert A. Mil-
likan’s Nobel Lecture, The Elec-
tron and the Light-Quanta from
the Experimental Point of View,
The Nobel Foundation, 1923.

quantum theory for the specific heat of matter, which takes into account the
quantization of lattice vibrational modes, was subsequently given by Debye
and Einstein.

1.1.2 Photoelectric effect

We turn now to the second ground-breaking experiment in the development of
quantum theory. When a metallic surface is exposed to electromagnetic radi-
ation, above a certain threshold frequency, the light is absorbed and electrons
are emitted (see figure, right). In 1902, Philipp Eduard Anton von Lenard
observed that the energy of individual emitted electrons increases with the
frequency of the light. This was at odds with Maxwell’s wave theory of light,
which predicted that the electron energy would be proportional to the intensity
of the radiation.
In 1905, Einstein resolved this paradox by describing light as composed of
discrete quanta (photons), rather than continuous waves. Based upon Planck’s
theory of black-body radiation, Einstein theorized that the energy in each
quantum of light was proportional to the frequency. A photon above a thresh- Robert Andrews Millikan 1868-
old energy, the “work function” W of the metal, has the required energy to 1953
He received
eject a single electron, creating the observed effect. In particular, Einstein’s his doctorate
theory was able to predict that the maximum kinetic energy of electrons emit- from Columbia
University and
ted by the radiation should vary as taught physics
at the University
k.e.max = hν − W . of Chicago
(1896-1921)
and the Cali-
Later, in 1916, Millikan was able to measure the maximum kinetic energy of fornia Institute
the emitted electrons using an evacuated glass chamber. The kinetic energy of of Technology (from 1921). To
measure electric charge, he devised
the photoelectrons were found by measuring the potential energy of the electric the Millikan oil-drop experiment. He
field, eV , needed to stop them. As well as confirming the linear dependence of verified Albert Einstein’s photoelec-
the kinetic energy on frequency (see Fig. 1.2), by making use of his estimate tric equation and obtained a precise
value for the Planck constant. He
for the electron charge, e, established from his oil drop experiment in 1913, he was awarded the 1923 Nobel Prize in
was able to determine Planck’s constant to a precision of around 0.5%. This physics.

discovery led to the quantum revolution in physics and earned Einstein the Arthur Holly Compton 1892-
Nobel Prize in 1921. 1962:
An American
physicist, he
1.1.3 Compton Scattering shared the 1927
Nobel Prize in
In 1923, Compton investigated the scattering of high energy X-rays and γ-ray Physics with C.
T. R. Wilson for
from electrons in a carbon target. By measuring the spectrum of radiation at his discovery of
different angles relative to the incident beam, he found two scattering peaks. the Compton ef-
fect. In addition
The first peak occurred at a wavelength which matched that of the incident to his work on
beam, while the second varied with angle. Within the framework of a purely X rays he made valuable studies of
classical theory of the scattering of electromagnetic radiation from a charged cosmic rays and contributed to the
development of the atomic bomb.

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1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 4

particle – Thomson scattering – the wavelength of a low-intensity beam should

remain unchanged.3
Compton’s observation demonstrated that light cannot be explained purely
as a classical wave phenomenon. Light must behave as if it consists of particles
in order to explain the low-intensity Compton scattering. If one assumes that
the radiation is comprised of photons that have a well defined momentum as
well as energy, p = hνc = λ , the shift in wavelength can be understood: The
h

interaction between electrons and high energy photons (ca. keV) results in
the electron being given part of the energy (making it recoil), and a photon
with the remaining energy being emitted in a different direction from the
original, so that the overall momentum of the system is conserved. By taking
into account both conservation of energy and momentum of the system, the
Compton scattering formula describing the shift in the wavelength as function
of scattering angle θ can be derived,4

h Figure 1.3: Variation of the

∆λ = λ# − λ = (1 − cos θ) . wavelength of X rays scattered
me c from a Carbon target. A. H.
Compton, Phys. Rev. 21, 483;
The constant of proportionality h/me c = 0.002426 nm, the Compton wave- 22, 409 (1923)
length, characterizes the scale of scattering. Moreover, as h → 0, one finds
that ∆λ → 0 leading to the classical prediction.

1.1.4 Atomic spectra

The discovery by Rutherford that the atom was comprised of a small positively
charged nucleus surrounded by a diffuse cloud of electrons lead naturally to the
consideration of a planetary model of the atom. However, a classical theory
of electrodynamics would predict that an accelerating charge would radiate Ernest Rutherford, 1st Baron
energy leading to the eventual collapse of the electron into the nucleus. More- Rutherford of Nelson, 1871-
over, as the electron spirals inwards, the emission would gradually increase 1937
in frequency leading to a broad continuous spectra. Yet, detailed studies of was
Zealand
a New
born
electrical discharges in low-pressure gases revealed that atoms emit light at British chemist
discrete frequencies. and Physicist
who became
The clue to resolving these puzzling observations lay in the discrete nature known as the
of atomic spectra. For the hydrogen atom, light emitted when the atom is father of nuclear
physics. He
thermally excited has a particular pattern: Balmer had discovered in 1885 discovered that
that the emitted wavelengths follow the empirical law, λ = λ0 (1/4 − 1/n2 ) atoms have a
small charged nucleus, and thereby
where n = 3, 4, 5, · · · and λ0 = 3645.6Å (see Fig. 1.4). Neils Bohr realized pioneered the Rutherford model
that these discrete vaues of the wavelength reflected the emission of individual (or planetary model of the atom,
photons having energy equal to the energy difference between two allowed through his discovery of Rutherford
scattering. He was awarded the
orbits of the electron circling the nucleus (the proton), En − Em = hν, leading Nobel Prize in Chemistry in 1908.
to the conclusion that the allowed energy levels must be quantized and varying He is widely credited as splitting the
atom in 1917 and leading the first
as En = − hcRn2
H
, where RH = 109678 cm−1 denotes the Rydberg constant. experiment to “split the nucleus” in
a controlled manner by two students
3
Classically, light of sufficient intensity for the electric field to accelerate a charged particle under his direction, John Cockcroft
to a relativistic speed will cause radiation-pressure recoil and an associated Doppler shift of and Ernest Walton in 1932.
the scattered light. But the effect would become arbitrarily small at sufficiently low light
intensities regardless of wavelength.
4
If we assume that the total energy and momentum are conserved in the scattering of a
photon (γ) from an initially stationary target electron (e), we have Eγ + Ee = Eγ ! + Ee!
and pγ = pγ ! + pe! . Here Eγ = hν and Ee = me c2 denote p the energy of the photon
and electron before the collision, while Eγ ! = hν # and Ee! = (pe! c)2 + (mc2 )2 denote the
energies after. From the equation for energy conservation, one obtains (pe! c)2 = (h(ν −
ν # ) + me c2 )2 − (me c2 )2 . From the equation for momentum conservation, one obtains p2e! =
p2γ + p2γ ! − 2|pγ ||pγ ! | cos θ. Then, noting that Eγ = pγ c, a rearrangement of these equations
obtains the Compton scattering formula.

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1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 5

Figure 1.4: Schematic describ-

ing various transitions (and an
image with the corresponding
visible spectral lines) of atomic
hydrogen.

How could the quantum hν restricting allowed radiation energies also re- Niels Henrik David Bohr 1885-
strict the allowed electron orbits? In 1913 Bohr proposed that the angular 1962
A Danish physi-
momentum of an electron in one of these orbits was quantized in units of cist who made
Planck’s constant, fundamental
contributions
to the un-
h
L = me vr = n!, != . (1.2) derstanding
2π atomic structure
and quantum
2 2 mechanics, for
As a result, one finds that RH = ( 4π$
e
0
)2 2πch3m . which he received
the Nobel Prize in Physics in 1922.
Bohr mentored and collaborated
( Exercise. Starting with the Bohr’s planetary model for atomic hydrogen, with many of the top physicists
find how the quantization condition (1.2) restricts the radius of the allowed (circular) of the century at his institute in
orbits. Determine the allowed energy levels and obtain the expression for the Rydberg Copenhagen. He was also part of the
team of physicists working on the
constant above. Manhattan Project. Bohr married
Margrethe Norlund in 1912, and one
of their sons, Aage Niels Bohr, grew
But why should only certain angular momenta be allowed for the circling up to be an important physicist who,
electron? A heuristic explanation was provided by de Broglie: just as the like his father, received the Nobel
prize, in 1975.
constituents of light waves (photons) are seen through Compton scattering
to act like particles (of definite energy and momentum), so particles such as
electrons may exhibit wave-like properties. For photons, we have seen that Louis Victor Pierre Raymond,
the relationship between wavelength and momentum is p = h/λ. de Broglie 7th duc de Broglie 1892-1987
hypothesized that the inverse was true: for particles with a momentum p, the A French physi-
cist, de Broglie
wavelength is had a mind of
a theoretician
h rather than
λ= , i.e. p = !k , (1.3) one of an
p experimenter
or engineer.
where k denotes the wavevector of the particle. Applied to the electron in de
1924
Broglie’s
doctoral
the atom, this result suggested that the allowed circular orbits are standing thesis Recherches sur la théorie des
waves, from which Bohr’s angular momentum quantization follows. The de quanta introduced his theory of
electron waves. This included the
Broglie hypothesis found quantitative support in an experiment by Davisson particle-wave property duality theory
and Germer, and independently by G. P. Thomson in 1927. Their studies of matter, based on the work of
Einstein and Planck. He won the
of electron diffraction from a crystalline array of Nickel atoms (Fig. 1.5) con- Nobel Prize in Physics in 1929 for
firmed that the diffraction angles depend on the incident energy (and therefore his discovery of the wave nature of
electrons, known as the de Broglie
momentum). hypothesis or mécanique ondulatoire.
This completes the summary of the pivotal conceptual insights that paved
the way towards the development of quantum mechanics.

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1.2. WAVE MECHANICS 6

Figure 1.5: In 1927, Davisson and Germer bombarded a single crystal of nickel
with a beam of electrons, and observed several beams of scattered electrons that
were almost as well defined as the incident beam. The phenomenological similarities
with X-ray diffraction were striking, and showed that a wavelength could indeed be
associated with the electrons. The first figure shows the intensity of electron scattering
against co-latitude angle for various bombarding voltages. The second figure shows
the intensity of electron scattering vs. azimuth angle - 54V, co-latitude 50. Figures
taken taken from C. Davisson and L. H. Germer, Reflection of electrons by a crystal
of nickel, Nature 119, 558 (1927).

1.2 Wave mechanics

de Broglie’s doctoral thesis, defended at the end of 1924, created a lot of
excitement in European physics circles. Shortly after it was published in
the Autumn of 1925, Pieter Debye, a theorist in Zurich, suggested to Erwin
Schrödinger that he give a seminar on de Broglie’s work. Schrödinger gave a
polished presentation, but at the end, Debye remarked that he considered the
whole theory rather childish: Why should a wave confine itself to a circle in
space? It wasnt as if the circle was a waving circular string; real waves in space
diffracted and diffused; in fact they obeyed three-dimensional wave equations,
and that was what was needed. This was a direct challenge to Schrödinger,
who spent some weeks in the Swiss mountains working on the problem, and
constructing his equation.
There is no rigorous derivation of Schrödinger’s equation from previously James Clerk Maxwell 1831-1879
was a Scottish
established theory, but it can be made very plausible by thinking about the theoretical
connection between light waves and photons, and constructing an analogous physicist and
structure for de Broglie’s waves and electrons (and, of course, other particles). mathematician.
His greatest
achievement was
the development
1.2.1 Maxwell’s wave equation of classical
electromagnetic
For a monochromatic wave in vacuum, with no currents or charges present, theory, synthesizing all previous
Maxwell’s wave equation, unrelated observations of electric-
ity, magnetism and optics into
a consistent theory. Maxwell’s
1
∇2 E − Ë = 0 , (1.4) equations demonstrated that elec-
c2 tricity, magnetism and light are all
manifestations of electromagnetic
field.
admits the plane wave solution, E = E0 ei(k·r−ωt) , with the linear dispersion
relation ω = c|k| and c the velocity of light. Here, (and throughout the text)
we adopt the convention, Ë ≡ ∂t2 E. We know from the photoelectric effect
and Compton scattering that the photon energy and momentum are related
to the frequency and wavelength of light through the relations E = hν = !ω,
p = λh = !k. The wave equation tells us that ω = c|k| and hence E = c|p|.
If we think of ei(k·r−ωt) as describing a particle (photon) it would be more
natural to write the plane wave in terms of the energy and momentum of the

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1.2. WAVE MECHANICS 7

particle as E0 ei(p·r−Et)/!. Then, one may see that the wave equation applied
to the plane wave describing particle propagation yields the familiar energy-
momentum relationship, E 2 = (cp)2 for a massless relativistic particle.
This discussion suggests how one might extend the wave equation from
the photon (with zero rest mass) to a particle with rest mass m0 . We require
a wave equation that, when it operates on a plane wave, yields the relativis-
tic energy-momentum invariant, E 2 = (cp)2 + m20 c4 . Writing the plane wave
function φ(r, t) = Aei(p·r−Et)/!, where A is a constant, we can recover the
energy-momentum invariant by adding a constant mass term to the wave op-
erator,
" # $ %
∂t2 m20 c2 (cp)2 − E 2 + m20 c4 i(p·r−Et)/!
2
∇ − 2 − 2 ei(p·r−Et)/!
=− e = 0.
c ! (!c)2

This wave equation is called the Klein-Gordon equation and correctly de-
scribes the propagation of relativistic particles of mass m0 . However, its form
is seems inappropriate for non-relativistic particles, like the electron in hydro-
gen.
Continuing along the same lines, let us assume that a non-relativistic elec-
tron in free space is also described by a plane wave of the form Ψ(x, t) =
Aei(p·r−Et)/!. We need to construct an operator which, when applied to this
wave function, just gives us the ordinary non-relativistic energy-momentum
p2
relation, E = 2m . The factor of p2 can obviously be recovered from two
derivatives with respect to r, but the only way we can get E is by having a
single differentiation with respect to time, i.e.

!2 2
i!∂t Ψ(r, t) = − ∇ Ψ(r, t) .
2m
This is Schrödinger’s equation for a free non-relativistic particle. One remark-
able feature of this equation is the factor of i which shows that the wavefunc-
tion is complex.
How, then, does the presence of a spatially varying scalar potential effect
the propagation of a de Broglie wave? This question was considered by Som-
merfeld in an attempt to generalize the rather restrictive conditions in Bohr’s Arnold Johannes Wilhelm Som-
model of the atom. Since the electron orbit was established by an inverse- merfeld 1868-1951
A German the-
square force law, just like the planets around the Sun, Sommerfeld couldn’t oretical physicist
understand why Bohr’s atom had only circular orbits as opposed to Kepler- who pioneered
developments
like elliptical orbits. (Recall that all of the observed spectral lines of hydrogen in atomic
were accounted for by energy differences between circular orbits.) and quantum
de Broglie’s analysis of the allowed circular orbits can be formulated by physics, and also
educated and
assuming that, at some instant, the spatial variation of the wavefunction on groomed a large
going around the orbit includes a phase term of the form eipq/!, where here number of students for the new era
of theoretical physics. He introduced
the parameter q measures the spatial distance around the orbit. Now, for an the fine-structure constant into
acceptable wavefunction, the total phase change on going around the orbit quantum mechanics.
must be 2πn, where n is integer. For the usual Bohr circular orbit, where
p = |p| is constant, this leads to quantization of the angular momentum
L = pr = n!.
Sommerfeld considered a general Keplerian elliptical orbit. Assuming that
the de Broglie relation p = h/λ still holds, the wavelength must vary as the par-
ticle moves around the orbit, being shortest where the particle travels fastest,
at its closest approach to the nucleus. Nevertheless, the phase change on mov-
ing a short distance ∆q should still be p∆q/!. Requiring the wavefunction to
link up smoothly on going once around the orbit gives the Bohr-Sommerfeld

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1.2. WAVE MECHANICS 8

quantization condition
&
p dq = nh , (1.5)

'
where denotes the line integral around a closed orbit. Thus only certain
elliptical orbits are allowed. The mathematics is non-trivial, but it turns out
that every allowed elliptical orbit has the same energy as one of the allowed
circular orbits. That is why Bohr’s theory gave the correct energy levels.
This analysis suggests that, in a varying potential, the wavelength changes in
concert with the momentum.

( Exercise. As a challenging exercise, try to prove Sommerfeld’s result for the

elliptical orbit.

1.2.2 Schrödinger’s equation

Following Sommerfeld’s considerations, let us then consider a particle moving
in one spatial dimension subject to a “roller coaster-like” potential. How do
we expect the wavefunction to behave? As discussed above, we would expect
the wavelength to be shortest where the potential is lowest, in the minima,
because that’s where the particle is going the fastest. Our task then is to
construct a wave equation which leads naturally to the relation following from Erwin Rudolf Josef Alexander
p2
(classical) energy conservation, E = 2m +V (x). In contrast to the free particle Schrdinger 1887-1961
was an Austrian
case discussed above, the relevant wavefunction here will no longer be a simple theoretical
plane wave, since the wavelength (determined through the momentum via the physicist who
achieved fame
de Broglie relation) varies with the potential. However, at a given position for his contribu-
x, the momentum is determined by the “local wavelength”. The appropriate tions to quantum
wave equation is the one-dimensional Schrödinger equation, mechanics,
especially the
Schrödinger
!2 ∂x2 equation, for
i!∂t Ψ(x, t) = − Ψ(x, t) + V (x)Ψ(x, t) , (1.6) which he received the Nobel Prize
2m in 1933. In 1935, after extensive
correspondence with personal
with the generalization to three-dimensions leading to the Laplacian operator friend Albert Einstein, he proposed
the Schrödinger’s cat thought
in place of ∂x2 (cf. Maxwell’s equation). experiment.
So far, the validity of this equation rests on plausibility arguments and
hand-waving. Why should anyone believe that it really describes an electron
wave? Schrödinger’s test of his equation was the hydrogen atom. He looked
for Bohr’s “stationary states”: states in which the electron was localized some-
where near the proton, and having a definite energy. The time dependence
would be the same as for a plane wave of definite energy, e−iEt/!; the spatial
dependence would be a time-independent function decreasing rapidly at large
distances from the proton. From the solution of the stationary wave equation
for the Coulomb potential, he was able to deduce the allowed values of en-
ergy and momentum. These values were exactly the same as those obtained
by Bohr (except that the lowest allowed state in the “new” theory had zero
angular momentum): impressive evidence that the new theory was correct.

1.2.3 Time-independent Schrödinger equation

As with all second order linear differential equations, if the potential V (x, t) =
V (x) is time-independent, the time-dependence of the wavefunction can be

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1.2. WAVE MECHANICS 9

separated from the spatial dependence. Setting Ψ(x, t) = T (t)ψ(x), and sep-
arating the variables, the Schrödinger equation takes the form,
( 2 2 )
− !2m
∂x
ψ(x) + V (x)ψ(x) i!∂t T (t)
= = const. = E .
ψ(x) T (t)
Since we have a function of only x set equal to a function of only t, they
both must equal a constant. In the equation above, we call the constant E
(with some knowledge of the outcome). We now have an equation in t set
equal to a constant, i!∂t T (t) = ET (t), which has a simple general solution,
T (t) = Ce−iEt/!, where C is some constant. The corresponding equation
in x is then given by the stationary, or time-independent Schrödinger
equation,

!2 ∂x2
− ψ(x) + V (x)ψ(x) = Eψ(x) .
2m

The full time-dependent solution is given by Ψ(x, t) = e−iEt/!ψ(x) with def-

inite energy, E. Their probability density |Ψ(x, t)|2 = |ψ(x)|2 is constant in
time – hence they are called stationary states! The operator

!2 ∂x2
Ĥ = − + V (x)
2m
defines the Hamiltonian and the stationary wave equation can be written as
the eigenfunction equation, Ĥψ(x) = Eψ(x), i.e. ψ(x) is an eigenstate of Ĥ
with eigenvalue E.

1.2.4 Particle flux and conservation of probability

In analogy to the Poynting vector for the electromagnetic field, we may want
to know the probability current. For example, for a free particle system, the
probability density is uniform over all space, but there is a net flow along the
direction of momentum. We can derive an equation showing conservation of
probability by differentiating the probability density, P (x, t) = |ψ(x, t)|2 , and
using the Schrödinger equation, ∂t P (x, t)+∂x j(x, t) = 0. This translates to the
usual conservation equation if j(x, t) is identified as the probability current,
i! ∗
j(x, t) = − [ψ ∂x ψ − ψ∂x ψ ∗ ] . (1.7)
2m
*b *b
If we integrate over some interval in x, a ∂t P (x, t)dx = − a ∂x j(x, t)dx it
*b
follows that ∂t a P (x, t)dx = j(x = a, t) − j(x = b, t), i.e. the rate of change
of probability is equal to the net flux entering the interval.
Extending this analysis to three space dimensions, we obtain the continuity
equation, ∂t P (r, t) + ∇ · j(r, t) = 0, from which follows the particle flux,

i! ∗
j(r, t) = − [ψ (r, t)∇ψ(r, t) − ψ(r, t)∇ψ ∗ (r, t)] . (1.8)
2m
This completes are survey of the foundations and development of quantum
theory. In due course, it will be necessary to develop some more formal math-
ematical aspects of the quantum theory. However, before doing, it is useful to
acquire some intuition for the properties of the Schrödinger equation. There-
fore, in the next chapter, we will explore the quantum mechanics of bound
and unbound particles in a one-dimensional system turning to discuss more
theoretical aspects of the quantum formulation in the following chapter.

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Chapter 2

Quantum mechanics in one

dimension

Following the rules of quantum mechanics, we have seen that the state of
a quantum particle, subject to a scalar potential V (r), is described by the
time-dependent Schrödinger equation,

i!∂t Ψ(r, t) = ĤΨ(r, t) , (2.1)

where Ĥ = − !2m
2 2
∇
+ V (r) denotes the Hamiltonian. To explore its proper-
ties, we will first review some simple and, hopefully, familiar applications of
the equation to one-dimensional systems. In addressing the one-dimensional
geometry, we will divide our consideration between potentials, V (x), which
leave the particle free (i.e. unbound), and those that bind the particle to some
region of space.

2.1 Wave mechanics of unbound particles

2.1.1 Free particle
In the absence of an external potential, the time-dependent Schrödinger equa-
tion (2.1) describes the propagation of travelling waves. In one dimension, the
corresponding complex wavefunction has the form

Ψ(x, t) = A ei(kx−ωt) ,

where A is the amplitude, and E(k) = !ω(k) = !2m

2 2
k
represents the free particle
energy dispersion for a non-relativistic particle of mass, m, and wavevector
k = 2π/λ with λ the wavelength. Each wavefunction describes a plane wave
in which the particle has definite energy E(k) and, in accordance with the
de Broglie relation, momentum p = !k = h/λ. The energy spectrum of a
freely-moving particle is therefore continuous, extending from zero to infinity
and, apart from the spatially constant state k = 0, has a two-fold degeneracy
corresponding to right and left moving particles.
For an infinite system, it makes no sense to fix the amplitude A by the
normalization of the total probability. Instead, it is useful to fix the flux
associated with the wavefunction. Making use of Eq. (1.7) for the particle
current, the plane wave is associated with a constant (time-independent) flux,

i! !k p
j(x, t) = − (Ψ∗ ∂x Ψ − c.c.) = |A|2 = |A|2 .
2m m m

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2.1. WAVE MECHANICS OF UNBOUND PARTICLES 11

For a given value of the!flux j, the amplitude is given, up to an arbitrary

constant phase, by A = mj/!k.
To prepare a wave packet which is localized to a region of space, we must
superpose components of different wave number. In an open system, this may
be achieved using a Fourier expansion. For any function,1 ψ(x), we have the
Fourier decomposition,2
" ∞
1
ψ(x) = √ ψ(k) eikx dk ,
2π −∞
where the coefficients are defined by the inverse transform,
" ∞
1
ψ(k) = √ ψ(x) e−ikx dx .
2π −∞
The normalization
#∞ ∗ of ψ(k) #follows automatically from the normalization of
∞
ψ(x), −∞ ψ (k)ψ(k)dk = −∞ ψ ∗ (x)ψ(x)dx = 1, and both can represent
probability amplitudes. Applied to a wavefunction, ψ(x) can be understood
as a wave packet made up of contributions involving definite momentum states,
eikx , with amplitude set by the Fourier coefficient ψ(k). The probability for a
particle to be found in a region of width dx around some value of x is given by
|ψ(x)|2 dx. Similarly, the probability for a particle to have wave number k in a
region of width dk around some value of k is given by |ψ(k)|2 dk. (Remember
that p = !k so the momentum distribution is very closely related. Here, for
economy of notation, we work with k.)
The Fourier transform of a normalized Gaussian wave packet, ψ(k) =
( 2α )1/4 e−α(k−k0 )2 , is also a Gaussian (exercise),
π
$ %1/4
1 x2
ψ(x) = eik0 x e− 4α .
2πα
From these representations, we can see that it is possible to represent a single
particle, localized in real space as a superposition of plane wave states localized
in Fourier space. But note that, while we have achieved our goal of finding
localized wave packets, this has been at the expense of having some non-zero
width in x and in k.
For the Gaussian wave packet, we can straightforwardly obtain the width
(as measured by the root mean square – RMS) of the probability distribution,
√
∆x = (#(x − #x$)2 $)1/2 ≡ (#x2 $ − #x$2 $)1/2 = α, and ∆k = √14α . We can
again see that, as we vary the width in k-space, the width in x-space varies
to keep the following product constant, ∆x∆k = 12 . If we translate from the
wavevector into momentum p = !k, then ∆p = !∆k and
!
∆p ∆x = .
2
If we consider the width of the distribution as a measure of the “uncertainty”,
we will prove in section (3.1.2) that the Gaussian wave packet provides the
minimum uncertainty. This result shows that we cannot know the position of
a particle and its momentum at the same time. If we try to localize a particle
to a very small region of space, its momentum becomes uncertain. If we try to
1
More precisely, we can make such an expansion providing we meet some rather weak
conditions of smoothness and differentiability of ψ(x) – conditions met naturally by problems
which derive from physical systems!
2
Here we will adopt an ecomony of notation using the same symbol ψ to denote the
wavefunction and its Fourier coefficients. Their identity will be disclosed by their argument
and context.

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2.1. WAVE MECHANICS OF UNBOUND PARTICLES 12

make a particle with a definite momentum, its probability distribution spreads

out over space.
With this introduction, we now turn to consider the interaction of a par-
ticle with a non-uniform potential background. For non-confining potentials,
such systems fall into the class of scattering problems: For a beam of par-
ticles incident on a non-uniform potential, what fraction of the particles are
transmitted and what fraction are reflected? In the one-dimensional system,
the classical counterpart of this problem is trivial: For particle energies which
exceed the maximum potential, all particles are eventually transmitted, while
for energies which are lower, all particles are reflected. In quantum mechan-
ics, the situation is richer: For a generic potential of finite extent and height,
some particles are always reflected and some are always transmitted. Later,
in chapter 14, we will consider the general problem of scattering from a lo-
calized potential in arbitrary dimension. But for now, we will focus on the
one-dimensional system, where many of the key concepts can be formulated.

2.1.2 Potential step

As we have seen, for a time-independent potential, the wavefunction can be
factorized as Ψ(x, t) = e−iEt/!ψ(x), where ψ(x) is obtained from the stationary
form of the Schrödinger equation,
& 2 2 '
! ∂x
− + V (x) ψ(x) = Eψ(x) ,
2m

and E denotes the energy of the particle. As |Ψ(x, t)|2 represents a probablility
density, it must be everywhere finite. As a result, we can deduce that the
wavefunction, ψ(x), is also finite. Moreover, since E and V (x) are presumed
finite, so must be ∂x2 ψ(x). The latter condition implies that

' both ψ(x) and ∂x ψ(x) must be continuous functions of x, even if V has
a discontinuity.

Consider then the influence of a potential step (see figure) on the prop-
agation of a beam of particles. Specifically, let us assume that a beam of
particles with kinetic energy, E, moving from left to right are incident upon a
potential step of height V0 at position x = 0. If the beam has unit amplitude,
the reflected and transmitted (complex) amplitudes are set by r and t. The
corresponding wavefunction is given by

ψ< (x) = eik< x + re−ik< x x < 0

ψ> (x) = teik> x x>0
( (
where k< = 2mE
!2
and k> = 2m(E−V !2
0)
. Applying the continuity conditions
on ψ and ∂x ψ at the step (x = 0), one obtains the relations 1 + r = t and
ik< (1 − r) = ik> t leading to the reflection and transmission amplitudes,

k< − k> 2k<

r= , t= .
k< + k> k< + k>
The reflectivity, R, and transmittivity, T , are defined by the ratios,
reflected flux transmitted flux
R= , T = .
incident flux incident flux

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2.1. WAVE MECHANICS OF UNBOUND PARTICLES 13

With the incident, reflected, and transmitted fluxes given by |A|2 !km< , |Ar|2 !km< ,
and |At|2 !km> respectively, one obtains
) ) ) )
) k< − k> )2 ) 2k< )2 k> 2 k> 4k< k>
R = )) ) = |r|2 , T = ) )
) k< + k> ) k< = |t| k< = (k< + k> )2 .
k< + k> )
From these results one can confirm that the total flux is, as expected, conserved
in the scattering process, i.e. R + T = 1.

' Exercise. While E −V0 remains positive, show that the beam is able to prop-
agate across the potential step (see figure). Show that the fraction of the beam that
is reflected depends on the relative height of the step while the phase depends on the
sign of V0 . In particular, show that for V0 > 0, the reflected beam remains in phase
with the incident beam, while for V0 < 0 it is reversed. Finally, when E − V0 < 0,
show that the beam is unable to propagate to the right (R = 1). Instead show that
there is an evanescent decay of the wavefunction into the barrier region with a decay
!
length set by 2π !2 /2m(V0 − E). If V0 → ∞, show that the system forms a standing
wave pattern.

2.1.3 Potential barrier

Having dealt with the potential step, we now turn to consider the problem
of a beam of particles incident upon a square potential barrier of height V0
(presumed positive for now) and width a. As mentioned above, this geometry
is particularly important as it includes the simplest example of a scattering
phenomenon in which a beam of particles is “deflected” by a local potential.
Moreover, this one-dimensional geometry also provides a platform to explore
a phenomenon peculiar to quantum mechanics – quantum tunneling. For
these reasons, we will treat this problem fully and with some care.
Since the barrier is localized to a region of size a, the incident and(trans-
mitted wavefunctions have the same functional form, eik1 x , where k1 = 2mE!2
,
and differ only in their complex amplitude, i.e. after the encounter with the
barrier, the transmitted wavefunction undergoes only a change of amplitude
(some particles are reflected from the barrier, even when the energy of the
incident beam, E, is in excess of V0 ) and a phase shift. To deterimine the rel-
ative change in amplitude and phase, we can parameterise the wavefunction
as
ψ1 (x) = eik1 x + re−ik1 x x≤0
ψ2 (x) = Aeik2 x + Be−ik2 x 0 ≤ x ≤ a
ψ3 (x) = teik1 x a≤x
(
where k2 = 2m(E−V !2
0)
. Here, as with the step, r denotes the reflected ampli-
tude and t the transmitted.
Applying the continuity conditions on the wavefunction, ψ, and its deriva-
tive, ∂x ψ, at the barrier interfaces at x = 0 and x = a, one obtains
* *
1+r =A+B k1 (1 − r) = k2 (A − B)
, .
Aeik2 a + Be−ik2 a = teik1 a k2 (Aeik2 a − Be−ik2 a ) = k1 teik1 a
Together, these four equations specify the four unknowns, r, t, A and B.
Solving, one obtains (exercise)

2k1 k2 e−ik1 a
t= ,
2k1 k2 cos(k2 a) − i(k12 + k22 ) sin(k2 a)

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2.1. WAVE MECHANICS OF UNBOUND PARTICLES 14

translating to a transmissivity of
1
T = |t|2 = + ,2 ,
1+ 1
4
k1
k2 − k2
k1 sin2 (k2 a)

and the reflectivity, R = 1 − T . As a consistency check, we can see that,

when V0 = 0, k2 = k1 and t = 1, as expected. Moreover, T is restricted to the
interval from 0 to 1 as required. So, for barrier heights in the range E > V0 > 0, Transmission probability of
a
√ finite potential barrier for
the transmittivity T shows an oscillatory behaviour with k2 reaching unity
2mV0 a/! = 7. Dashed: classi-
when k2 a = nπ with n integer. At these values, there is a conspiracy of cal result. Solid line: quantum
interference effects which eliminate altogether the reflected component of the mechanics.
wave leading to perfect transmission. Such a situation arises when the width
of the barrier is perfectly matched to an integer or half-integer number of
wavelengths inside the barrier.
When the energy of the incident particles falls below the energy of the
barrier, 0 < E < V0 , a classical beam would be completely reflected. How-
ever, in the quantum system, particles are able to tunnel through the bar-
rier region and escape leading to a non-zero transmission coefficient. In this
regime, k2 = iκ2 becomes pure imaginary leading to an evanescent decay of
the wavefunction under the barrier and a suppression, but not extinction, of
transmission probability,
1
T = |t|2 = + ,2 .
1+ 1
4
k1
κ2 + κ2
k1 sinh2 κ2 a

For κ2 a ) 1 (the weak tunneling limit), the transmittivity takes the form
16k12 κ22 −2κ2 a
T * e .
(k12 + κ22 )2
Finally, on a cautionary note, while the phenomenon of quantum mechan-
ical tunneling is well-established, it is difficult to access in a convincing exper- Real part of the wavefunction for
imental manner. Although a classical particle with energy E < V0 is unable E/V0 = 0.6 (top), E/V0 = 1.6
to penetrate the barrier region, in a physical setting, one is usually concerned (middle), and E/V0 = 1 + π 2 /2
with a thermal distribution of particles. In such cases, thermal activation (bottom), where mV0 a2 /!2 =
may lead to transmission over a barrier. Such processes often overwhelm any 1. In the first case, the system
contribution from true quantum mechanical tunneling. shows tunneling behaviour, while
in the third case, k2 a = π and
the system shows resonant trans-
' Info. Scanning tunneling microscopy (STM) is a powerful technique for
mission.
viewing surfaces at the atomic level. Its development in the early eighties earned
its inventors, Gerd Binnig and Heinrich Rohrer (at IBM Zürich), the Nobel Prize in
Physics in 1986. STM probes the density of states of a material using the tunneling
current. In its normal operation, a lateral resolution of 0.1 nm and a depth resolution
of 0.01 nm is typical for STM. The STM can be used not only in ultra-high vacuum,
but also in air and various other liquid or gas ambients, and at temperatures ranging
from near zero kelvin to a few hundred degrees Celsius.
The STM is based on the concept of quantum tunnelling (see Fig. 2.1). When a
STM image showing two point
conducting tip is brought in proximity to a metallic or semiconducting surface, a bias
defects adorning the copper
between the two can allow electrons to tunnel through the vacuum between them.
(111) surface. The point defects
For low voltages, this tunneling current is a function of the local density of states at (possibly impurity atoms) scat-
the Fermi level, EF , of the sample.3 Variations in current as the probe passes over ter the surface state electrons re-
the surface are translated into an image. STM can be a challenging technique, as it sulting in circular standing wave
requires extremely clean surfaces and sharp tips. patterns.

3
Although the meaning of the Fermi level will be address in more detail in chapter 8, we
mention here that it represents the energy level to which the electron states in a metal are
fully-occupied.

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2.2. WAVE MECHANICS OF BOUND PARTICLES 15

Figure 2.1: Principle of scanning tunneling microscopy: Applying a negative sample

voltage yields electron tunneling from occupied states at the surface into unoccupied
states of the tip. Keeping the tunneling current constant while scanning the tip over
the surface, the tip height follows a contour of constant local density of states.

2.1.4 The rectangular potential well

Finally, if we consider scattering from a potential well (i.e. with V0 < 0), while
E > 0, we can apply the results of the previous section to find a continuum
of unbound states with the corresponding resonance behaviour. However, in
addition to these unbound states, for E < 0 we have the opportunity to find
bound states of the potential. It is to this general problem that we now turn.

' Exercise. Explore the phase dependence of the transmission coefficient in

this regime. Consider what happens to the phase as resonances (bound states) of the
potential are crossed.

2.2 Wave mechanics of bound particles

In the case of unbound particles, we have seen that the spectrum of states
is continuous. However, for bound particles, the wavefunctions satisfying the
Schrödinger equation have only particular quantized energies. In the one-
dimensional system, we will find that all binding potentials are capable of
hosting a bound state, a feature particular to the low dimensional system.

2.2.1 The rectangular potential well (continued)

As a starting point, let us consider a rectangular potential well similar to that
discussed above. To make use of symmetry considerations, it is helpful to
reposition the potential setting

 0 x ≤ −a
V (x) = −V0 −a ≤ x ≤ a ,

0 a≤x

where the potential depth V0 is assumed positive. In this case, we will look
for bound state solutions with energies lying in the range −V0 < E < 0.
Since the Hamiltonian is invariant under parity transformation, [Ĥ, P̂ ] = 0
(where P̂ ψ(x) = ψ(−x)), the eigenstates of the Hamiltonian Ĥ must also be

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2.2. WAVE MECHANICS OF BOUND PARTICLES 16

eigenstates of parity, i.e. we expect the eigenfunctions to separate into those

symmetric and those antisymmetric under parity.4
For E < 0 (bound states), the wavefunction outside the well region must
have the form

ψ(x < −a) = Ceκx , ψ(x > a) = De−κx ,

(
with κ = − 2mE
!2
while in the central well region, the general solution is of
the form

ψ(−a < x < a) = A cos(kx) + B sin(kx) ,

(
where k = 2m(E+V !2
0)
. Once again we have four equations in four unknowns.
The calculation shows that either A or B must be zero for a solution. This
means that the states separate into solutions with even or odd parity.
For the even states, the solution of the equations leads to the quantization
condition, κ = tan(ka)k, while for the odd states, we find κ = − cot(ka)k.
These are transcendental equations, and must be solved numerically. The
2
figure (right) compares κa = ( 2mV!2
0a
− (ka)2 )1/2 with ka tan(ka) for the even
states and to −ka cot(ka) for the odd states. Where the curves intersect, we
have an allowed energy. From the structure of these equations, it is evident 2
that an even state solution can always be found for arbitrarily small values Comparison of κa = ( 2mV !2
0a
−
of the binding potential V0 while, for odd states, bound states appear only at (ka) )
2 1/2
with ka tan(ka) and
2
a critical value of the coupling strength. The wider and deeper the well, the −ka cot(ka) for 2mV !2
0a
= 14.
more solutions are generated. For this potential, there are a to-
tal of three solutions labelled A,
B and C. Note that, from the
' Exercise. Determine the pressure exerted on the walls of a rectangular po- geometry of the curves, there is
tential well by a particle inside. For a hint on how to proceed, see the discussion on always a bound state no matter
degeneracy pressure on page 85. how small is the potential V0 .

2.2.2 The δ-function potential well

Let us now consider perhaps the simplest binding potential, the δ-function,
V (x) = −aV0 δ(x). Here the parameter ‘a’ denotes some microscopic length
scale introduced to make the product aδ(x) dimensionless.5 For a state to
be bound, its energy must be negative. Moreover, the form of the potential
demands that the wavefunction is symmetric under parity, x → −x. (A wave-
function which was antisymmetric must have ψ(0) = 0 and so could not be
influenced by the δ-function potential.) We therefore look for a solution of the
form
* κx
e x<0
ψ(x) = A ,
e−κx x>0
!
where κ = −2mE/!2 . With this choice, the wavefunction remains every-
where continuous including at the potential, x = 0. Integrating the stationary
form of the Schrödinger equation across an infinitesimal interval that spans
the region of the δ-funciton potential, we find that
2maV0
∂x ψ|+% − ∂x ψ|−% = − ψ(0) .
!2
4
Later, in section 3.2, we will discuss the role of symmetries in quantum mechanics.
5
Note that the dimenions of δ(x) are [Length−1 ].

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2.2. WAVE MECHANICS OF BOUND PARTICLES 17

From this result, we obtain that κ = maV0 /!2 , leading to the bound state
energy

ma2 V02
E=− .
2!2
Indeed, the solution is unique. An attractive δ-function potential hosts only
one bound state.

' Exercise. Explore the bound state properties of the “molecular” binding
potential V (x) = −aV0 [δ(x + d) + δ(x − d)]. Show that it consists of two bound states,
one bonding (nodeless) and one antibonding (single node). How does the energy of
the latter compare with two isolated δ-function potential wells?

2.2.3 Info: The δ-function model of a crystal

Finally, as our last example of a one-dimensional quantum system, let us consider
a particle moving in a periodic potential. The Kronig-Penney model provides a
caricature of a (one-dimensional) crystalline lattice potential. The potential created
by the ions is approximated as an infinite array of potential wells defined by a set of
repulsive δ-function potentials,
∞
0
V (x) = aV0 δ(x − na) .
n=−∞

Since the potential is repulsive, it is evident that all states have energy E > 0.
This potential has a new symmetry; a translation by the lattice spacing a leaves
the protential unchanged, V (x + a) = V (x). The probability density must therefore
exhibit the same translational symmetry,

|ψ(x + a)|2 = |ψ(x)|2 ,

which means that, under translation, the wavefunction differs by at most a phase,
ψ(x + a) = eiφ ψ(x). In the region from (n − 1)a < x < na, the general solution of
the Schrödinger equation is plane wave like and can be written in the form,

ψn (x) = An sin[k(x − na)] + Bn cos[k(x − na)] ,

!
where k = 2mE/!2 and, following the constraint on translational invariance, An+1 =
eiφ An and Bn+1 = eiφ Bn . By applying the boundary conditions, one can derive a
constraint on k similar to the quantized energies for bound states considered above.
Consider the boundary conditions at position x = na. Continuity of the wave-
function, ψn |x=na = ψn+1 |x=na , translates to the condition, Bn = An+1 sin(−ka) +
Bn+1 cos(−ka) or

Bn + An+1 sin(ka)
Bn+1 = .
cos(ka)

Similarly, the discontinuity in the first derivative, ∂x ψn+1 |x=na −∂x ψn |na = 2maV
!2 ψn (na),
0

leads to the condition, k [An+1 cos(ka) + Bn+1 sin(ka) − An ] = !2 Bn . Substitut-

2maV0

ing the expression for Bn+1 and rearranging, one obtains

2maV0
An+1 = Bn cos(ka) − Bn sin(ka) + An cos(ka) .
!2 k
Similarly, replacing the expression for An+1 in that for Bn+1 , one obtains the parallel
equation,
2maV0
Bn+1 = Bn sin(ka) + Bn cos(ka) + An sin(ka) .
!2 k

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2.2. WAVE MECHANICS OF BOUND PARTICLES 18

With these two eqations, and the relations An+1 = eiφ An and Bn+1 = eiφ Bn , we
obtain the quantization condition,6

maV0
cos φ = cos(ka) + sin(ka) .
!2 k
√
As !k = 2mE, this result relates the allowed values of energy to the real parameter,
φ. Since cos φ can only take values between −1 and 1, there are a sequence of allowed
bands of energy with energy gaps separating these bands (see Fig. 2.2). Figure 2.2: Solid line shows the
Such behaviour is characteristic of the spectrum of periodic lattices: In the peri- variation of cos φ with ka over a
odic system, the wavefunctions – known as Bloch states – are indexed by a “quasi”- range from −1 to 1 for V0 = 2
momentum index k, and a band index n where each Bloch band is separated by an and ma2 !2 = 1. The blue line
energy gap within which there are no allowed states. In a metal, electrons (fermions) shows 0.01×E = (!k)2 /2m. The
populate the energy states starting with the lowest energy up to some energy scale shaded region represents values
of k and energy for which there
known as the Fermi energy. For a partially-filled band, low-lying excitations associ-
is no solution.
ated with the continuum of states allow electrons to be accelerated by a weak electric
field. In a band insulator, all states are filled up to an energy gap. In this case,
a small electric field is unable to excite electrons across the energy gap – hence the
system remains insulating.

' Exercise. In the Kronig-Penney model above, we took the potential to be

repulsive. Consider what happens if the potential is attractive when we also have to
consider the fate of the states that were bound for the single δ-function potential. In
this case, you will find that the methodology and conclusions mirror the results of the
repulsive potential: all states remain extended and the continuum of states exhibits
a sequence of band gaps controlled by similar sets of equations.

6
Eliminating An and Bn from the equations, a sequence of cancellations obtains
„ «
2maV0
e2iφ − eiφ sin(ka) + 2 cos(ka) + 1 = 0 .
! k
2

Then multiplying by e−iφ , we obtain the expression for cos φ.

Advanced Quantum Physics

Chapter 3

Operator methods in
quantum mechanics

While the wave mechanical formulation has proved successful in describing

the quantum mechanics of bound and unbound particles, some properties can
not be represented through a wave-like description. For example, the electron
spin degree of freedom does not translate to the action of a gradient operator.
It is therefore useful to reformulate quantum mechanics in a framework that
involves only operators.
Before discussing properties of operators, it is helpful to introduce a further
simplification of notation. One advantage of the operator algebra is that it
p̂2
does not rely upon a particular basis. For example, when one writes Ĥ = 2m ,
where the hat denotes an operator, we can equally represent the momentum
operator in the spatial coordinate basis, when it is described by the differential
operator, p̂ = −i!∂x , or in the momentum basis, when it is just a number
p̂ = p. Similarly, it would be useful to work with a basis for the wavefunction
which is coordinate independent. Such a representation was developed by
Dirac early in the formulation of quantum mechanics.
In the parlons of mathematics, square integrable functions (such as wave-
functions) are said form a vector space, much like the familiar three-dimensional
vector spaces. In the Dirac notation, a state vector or wavefunction, ψ, is
represented as a “ket”, |ψ". Just as we can express any three-dimensional
vector in terms of the basis vectors, r = xê1 + yê2 + zê3 , so we can expand
any wavefunction as a superposition of basis state vectors,

|ψ" = λ1 |ψ1 " + λ2 |ψ2 " + · · · .

Alongside the ket, we can define the “bra”, #ψ|. Together, the bra and ket
define the scalar product
! ∞
#φ|ψ" ≡ dx φ∗ (x)ψ(x) ,
−∞

from which follows the identity, #φ|ψ"∗ = #ψ|φ". In this formulation, the real
space representation of the wavefunction is recovered from the inner prod-
uct ψ(x) = #x|ψ" while the momentum space wavefunction is obtained from
ψ(p) = #p|ψ". As with a three-dimensional vector space where a · b ≤ |a| |b|,
the magnitude of the scalar product is limited by the magnitude of the vectors,
"
#ψ|φ" ≤ #ψ|ψ"#φ|φ" ,

a relation known as the Schwartz inequality.

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3.1. OPERATORS 20

3.1 Operators
An operator  is a “mathematical object” that maps one state vector, |ψ",
into another, |φ", i.e. Â|ψ" = |φ". If

Â|ψ" = a|ψ" ,

with a real, then |ψ" is said to be an eigenstate (or eigenfunction) of  with

eigenvalue a. For example, the plane wave state ψp (x) = #x|ψp " = A eipx/! is
an eigenstate of the momentum operator, p̂ = −i!∂x , with eigenvalue p.
For a free particle, the plane wave is also an eigenstate of the Hamiltonian,
p̂2 p2
Ĥ = 2m with eigenvalue 2m .
In quantum mechanics, for any observable A, there is an operator  which
acts on the wavefunction so that, if a system is in a state described by |ψ",
the expectation value of A is
! ∞
#A" = #ψ|Â|ψ" = dx ψ ∗ (x)Âψ(x) . (3.1)
−∞

Every operator corresponding to an observable is both linear and Hermitian:

That is, for any two wavefunctions |ψ" and |φ", and any two complex numbers
α and β, linearity implies that

Â(α|ψ" + β|φ") = α(Â|ψ") + β(Â|φ") .

Moreover, for any linear operator Â, the Hermitian conjugate operator
(also known as the adjoint) is defined by the relation
! !
#φ|Âψ" = dx φ∗ (Âψ) = dx ψ(† φ)∗ = #† φ|ψ" . (3.2)

From the definition, #† φ|ψ" = #φ|Âψ", we can prove some useful rela-
tions: Taking the complex conjugate, #† φ|ψ"∗ = #ψ|† φ" = #Âψ|φ", and
then finding the Hermitian conjugate of † , we have

#ψ|† φ" = #(† )† ψ|φ" = #Âψ|φ", i.e. († )† =  .

Therefore, if we take the Hermitian conjugate twice, we get back to the same
operator. Its easy to show that (λÂ)† = λ∗ † and ( + B̂)† = † + B̂ † just
from the properties of the dot product. We can also show that (ÂB̂)† = B̂ † †
from the identity, #φ|ÂB̂ψ" = #† φ|B̂ψ" = #B̂ † † φ|ψ". Note that operators
are associative but not (in general) commutative,

ÂB̂|ψ" = Â(B̂|ψ") = (ÂB̂)|ψ" =

& B̂ Â|ψ" .

A physical variable must have real expectation values (and eigenvalues).

This implies that the operators representing physical variables have some spe-
cial properties. By computing the complex conjugate of the expectation value
of a physical variable, we can easily show that physical operators are their own
Hermitian conjugate,
#! ∞ $∗ ! ∞
∗ ∗
#ψ|Ĥ|ψ" = ψ (x)Ĥψ(x)dx = ψ(x)(Ĥψ(x))∗ dx = #Ĥψ|ψ" .
−∞ −∞

i.e. #Ĥψ|ψ" = #ψ|Ĥψ" = #Ĥ † ψ|ψ", and Ĥ † = Ĥ. Operators that are their
own Hermitian conjugate are called Hermitian (or self-adjoint).

Advanced Quantum Physics

3.1. OPERATORS 21

' Exercise. Prove that the momentum operator p̂ = −i!∇ is Hermitian. Fur-
ther show that the parity operator, defined by P̂ ψ(x) = ψ(−x) is also Hermitian.

Eigenfunctions of Hermitian operators Ĥ|i" = Ei |i" form an orthonormal (i.e.

#i|j" = δij ) complete basis: For
% a complete set of states |i", we can expand
a state function |ψ" as |ψ" = i |i"#i|ψ".
% Equivalently, % in a coordinate rep-
resentation, we have ψ(x) = #x|ψ" = i #x|i"#i|ψ" = i #i|ψ"φi (x), where
φi (x) = #x|i".

' Info. Projection operators and completeness: A ‘ket’ state vector fol-
lowed by a ‘bra’ state vector is an example of an operator. The operator which
projects a vector onto the jth eigenstate is given by |j"#j|. First the bra vector dots
into the state, giving the coefficient of |j" in the state, then its multiplied by the unit
vector |j", turning it back into a vector, with the right length to be a projection. An
operator maps one vector into another vector, so this is an operator. If we sum over
a complete set of states, like the eigenstates of a Hermitian operator, we obtain the
(useful) resolution of identity
&
|i"#i| = I .
i
%
Again, in coordinate form, we can write i φ∗i (x)φi (x" ) = δ(x − x" ). Indeed, we can
%
form a projection operator into a subspace, P̂ = subspace |i"#i|.

As in a three-dimensional
% vector %
space, the expansion of the vectors |φ" and
|ψ", as |φ" = i bi |i" and |ψ" = i ci |i",%
allows the dot product to be taken
by multiplying the components, #φ|ψ" = i b∗i ci .

' Example: The basis states can be formed from any complete set of orthogonal
states. In particular, they can' be formed from' the basis states of the position or
∞ ∞
the momentum operator, i.e. −∞ dx|x"#x| = −∞ dp|p"#p| = I. If we apply these
definitions, we can then recover the familiar Fourier representation,
! ∞ ! ∞
1
ψ(x) ≡ #x|ψ" = dp #x|p" #p|ψ" = √ dp eipx/! ψ(p) ,
−∞ ( )* +
√ 2π! −∞
eipx/! / 2π!
where #x|p" denotes the plane wave state |p" expressed in the real space basis.

3.1.1 Time-evolution operator

The ability to develop an eigenfunction expansion provides the means to ex-
plore the time evolution of a general wave packet, |ψ" under the action of
a Hamiltonian. Formally, we can evolve a wavefunction forward in time
by applying the time-evolution operator. For a Hamiltonian which is time-
indepenent, we have |ψ(t)" = Û |ψ(0)", where

Û = e−iĤt/! ,

denotes
% the time-evolution operator. By inserting the resolution of identity,
1

I = i |i"#i|, where the states |i" are eigenstates of the Hamiltonian with
eigenvalue Ei , we find that
& &
|ψ(t)" = e−iĤt/! |i"#i|ψ(0)" = |i"#i|ψ(0)"e−iEi t/! .
i i
1
This equation follows from integrating the time-dependent Schrödinger equation, Ĥ|ψ! =
i!∂t |ψ!.

Advanced Quantum Physics

3.1. OPERATORS 22

p̂2
' Example: Consider the harmonic oscillator Hamiltonian Ĥ = + 12 mω 2 x2 .
2m
Later in this chapter, we will see that the eigenstates, |n", have equally-spaced eigen-
values, En = !ω(n + 1/2), for n = 0, 1, 2, · · ·. Let us then consider the time-evolution
of a general wavepacket, |ψ(0)", under
% the action of the Hamiltonian. From the equa-
tion above, we find that |ψ(t)" = n |n"#n|ψ(0)"e−iEn t/! . Since the eigenvalues are
equally spaced, let us consider what happens when t = tr ≡ 2πr/ω, with r integer.
In this case, since e2πinr = 1, we have
&
|ψ(tr )" = |n"#n|ψ(0)"e−iωtr /2 = (−1)r |ψ(0)" .
n

From this result, we can see that, up to an overall phase, the wave packet is perfectly
reconstructed at these times. This recurrence or “echo” is not generic, but is a
manifestation of the equal separation of eigenvalues in the harmonic oscillator.

' Exercise. Using the symmetry of the harmonic oscillator wavefunctions under
parity show that, at times tr = (2r + 1)π/ω, #x|ψ(tr )" = e−iωtr /2 #−x|ψ(0)". Explain
the origin of this recurrence.

The time-evolution operator is an example of a unitary operator. The

latter are defined as transformations which preserve the scalar product, #φ|ψ" =
!
#Û φ|Û ψ" = #φ|Û † Û ψ" = #φ|ψ", i.e.

Û † Û = I .

3.1.2 Uncertainty principle for non-commuting operators

For non-commuting Hermitian operators, [Â, B̂] &= 0, it is straightforward to
establish a bound on the uncertainty in their expectation values. Given a state
|ψ", the mean square uncertainty is defined as

(∆A)2 = #ψ|(Â − #Â")2 ψ" = #ψ|Û 2 ψ"

(∆B)2 = #ψ|(B̂ − #B̂")2 ψ" = #ψ|V̂ 2 ψ" ,

where we have defined the operators Û = Â − #ψ|Âψ" and V̂ = B̂ − #ψ|B̂ψ".

Since #Â" and #B̂" are just constants, [Û , V̂ ] = [Â, B̂]. Now let us take the
scalar product of Û |ψ" + iλV̂ |ψ" with itself to develop some information about
the uncertainties. As a modulus, the scalar product must be greater than or
equal to zero, i.e. expanding, we have #ψ|Û 2 ψ" + λ2 #ψ|V̂ 2 ψ" + iλ#Û ψ|V̂ ψ" −
iλ#V̂ ψ|Û ψ" ≥ 0. Reorganising this equation in terms of the uncertainties, we
thus find

(∆A)2 + λ2 (∆B)2 + iλ#ψ|[Û , V̂ ]|ψ" ≥ 0 .

If we minimise this expression with respect to λ, we can determine when

the inequality becomes strongest. In doing so, we find

i #ψ|[Û , V̂ ]|ψ"
2λ(∆B)2 + i#ψ|[Û , V̂ ]|ψ" = 0, λ=− .
2 (∆B)2

Substiuting this value of λ back into the inequality, we then find,

1
(∆A)2 (∆B)2 ≥ − #ψ|[Û , V̂ ]|ψ"2 .
4

Advanced Quantum Physics

3.1. OPERATORS 23

We therefore find that, for non-commuting operators, the uncertainties obey

the following inequality,

i
∆A ∆B ≥ #[Â, B̂]" .
2

If the commutator is a constant, as in the case of the conjugate operators

[p̂, x] = −i!, the expectation values can be dropped, and we obtain the rela-
tion, (∆A)(∆B) ≥ 2i [Â, B̂]. For momentum and position, this result recovers
Heisenberg’s uncertainty principle,

i !
∆p ∆x ≥ #[p̂, x]" = .
2 2

Similarly, if we use the conjugate coordinates of time and energy, [Ê, t] = i!,
we have

!
∆E ∆t ≥ .
2

3.1.3 Time-evolution of expectation values

Finally, to close this section on operators, let us consider how their expectation
values evolve. To do so, let us consider a general operator  which may itself
involve time. The time derivative of a general expectation value has three
terms.
d
#ψ|Â|ψ" = ∂t (#ψ|)Â|ψ" + #ψ|∂t Â|ψ" + #ψ|Â(∂t |ψ") .
dt
If we then make use of the time-dependent Schrödinger equation, i!∂t |ψ" =
Ĥ|ψ", and the Hermiticity of the Hamiltonian, we obtain

d i, -
#ψ|Â|ψ" = #ψ|Ĥ Â|ψ" − #ψ|ÂĤ|ψ" +#ψ|∂t Â|ψ" .
dt (! )* +
i
#ψ|[Ĥ, Â]|ψ"
!
This is an important and general result for the time derivative of expectation
values which becomes simple if the operator itself does not explicitly depend
on time,

d i
#ψ|Â|ψ" = #ψ|[Ĥ, Â]|ψ" .
dt !

From this result, which is known as Ehrenfest’s theorem, we see that expec-
tation values of operators that commute with the Hamiltonian are constants Paul Ehrenfest 1880-1933
An Austrian
of the motion. physicist and
mathematician,
' Exercise. Applied to the non-relativistic Schrödinger operator for a single who obtained
2
p̂ %p̂& ˙ = −#∂x V ". Dutch citizenship
particle moving in a potential, Ĥ = 2m + V (x), show that #ẋ" = m , #p̂" in 1922. He
Show that these equations are consistent with the relations, made major
. / . / contributions
d ∂H d ∂H to the field
#x" = , #p̂" = − , of statistical
dt ∂p dt ∂x mechanics and its relations with
quantum mechanics, including the
the counterpart of Hamilton’s classical equations of motion. theory of phase transition and the
Ehrenfest theorem.

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3.2. SYMMETRY IN QUANTUM MECHANICS 24

3.2 Symmetry in quantum mechanics

Symmetry considerations are very important in quantum theory. The struc-
ture of eigenstates and the spectrum of energy levels of a quantum system
reflect the symmetry of its Hamiltonian. As we will see later, the transition
probabilities between different states under a perturbation, such as that im-
posed by an external electromagnetic field, depend in a crucial way on the
transformation properties of the perturbation and lead to “selection rules”.
Symmetries can be classified into two types, discrete and continuous, accord-
ing to the transformations that generate them. For example, a mirror symme-
try is an example of a discrete symmetry while a rotation in three-dimensional
space is continuous.
Formally, the symmetries of a quantum system can be represented by a
group of unitary transformations (or operators), Û , that act in the Hilbert
space.2 Under the action of such a unitary transformation, operators corre-
sponding to observables  of the quantum model will then transform as,

 → Û † ÂÛ .

For unitary transformations, we have seen that Û † Û = I, i.e. Û † = Û −1 .

Under what circumstances does such a group of transformations represent a
symmetry group? Consider a Schrödinger particle in three dimensions:3
The basic observables are the position and momentum vectors, r̂ and p̂. We
can always define a transformation of the coordinate system, or the observ-
ables, such that a vector  = r̂ or p̂ is mapped to R[Â].4 If R is an element
of the group of transformations, then this transformation will be represented
by a unitary operator Û (R), such that

Û † ÂÛ = R[Â] .

Such unitary transformations are said to be symmetries of a general op-

erator Ô(p̂, r̂) if

Û † ÔÛ = Ô, i.e. [Ô, Û ] = 0 .

If Ô(p̂, r̂) ≡ Ĥ, the quantum Hamiltonian, such unitary transformations are
said to be symmetries of the quantum system.

3.2.1 Observables as generators of transformations

The vector operators p̂ and r̂ for a Schrödinger particle are themselves genera-
tors of space-time transformations. From the standard commutation relations
2
In quantum mechanics, the possible states of a system can be represented by unit vectors
(called “state vectors”) residing in “state space” known as the Hilbert space. The precise
nature of the Hilbert space is dependent on the system; for example, the state space for
position and momentum states is the space of square-integrable functions.
3
In the following, we will focus our considerations on the realm of “low-energy” physics
where the relevant space-time transformations belong to the Galilei group, leaving our
discussion of Lorentz invariance to the chapter on relativistic quantum mechanics.
4
e.g., for a clockwise spatial rotation by an angle θ around ez , we have,
0 1
cos θ sin θ 0
R[r] = Rij x̂j , R = @ − sin θ cos θ 0 A .
0 0 1

Similarly, for a spatial translation by a vector a, R[r] = r + a. (Exercise: construct repre-

sentations for transformations corresponding to spatial reflections, and inversion.)

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3.2. SYMMETRY IN QUANTUM MECHANICS 25

one can show that, for a constant vector a, the unitary operator
# $
i
Û (a) = exp − a · p̂ ,
!
acting in the Hilbert space of a Schrödinger particle performs a spatial trans-
lation, Û † (a)f (r)Û (a) = f (r + a), where f (r) denotes a general algebraic
function of r.

' Info. The proof runs as follows: With p̂ = −i!∇,

&∞
1
Û † (a) = ea·∇ = ai · · · ain ∇i1 · · · ∇in ,
n=0
n! 1

where summation on the repeated indicies, im is assumed. Then, making use of the
Baker-Hausdorff identity (exercise)

1
e B̂e− = B̂ + [Â, B̂] + [Â, [Â, B̂]] + · · · , (3.3)
2!
it follows that
1
Û † (a)f (r)Û (a) = f (r) + ai1 (∇i1 f (r)) + ai ai (∇i1 ∇i2 f (r)) + · · · = f (r + a) ,
2! 1 2
where the last identity follows from the Taylor expansion.

' Exercise. Prove the Baker-Hausdorff identity (3.3).

Therefore, a quantum system has spatial translation as an invariance group if

and only if the following condition holds,

Û (a)Ĥ = Ĥ Û (a), i.e. p̂Ĥ = Ĥ p̂ .

This demands that the Hamiltonian is independent of position, Ĥ = Ĥ(p̂),

as one might have expected! Similarly, the group of unitary transforma-
tions, Û (b) = exp[− !i b · r̂], performs translations in momentum space.
Moreover, spatial rotations are generated by the transformation Û (b) =
exp[− !i θen · L̂], where L̂ = r̂ × p̂ denotes the angular momentum operator.

' Exercise. For an infinitesimal rotation by an angle θ by a fixed axis, ên ,

construct R[r] and show that Û = I − !i θên · L + O(θ2 ). Making use of the identity
limN →∞ (1 − Na )N = e−a , show that “large” rotations are indeed generated by the
0 1
unitary transformations Û = exp − !i θên · L .

As we have seen, time translations are generated by the time evolution op-
erator, Û (t) = exp[− !i Ĥt]. Therefore, every observable which commutes with
the Hamiltonian is a constant of the motion (invariant under time transla-
tions),

Ĥ Â = ÂĤ ⇒ eiĤt/!Âe−iĤt/! = Â, ∀t .

We now turn to consider some examples of discrete symmetries. Amongst

these, perhaps the most important in low-energy physics are parity and time-
reversal. The parity operation, denoted P̂ , involves a reversal of sign on all
coordinates.

P̂ ψ(r) = ψ(−r) .

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3.2. SYMMETRY IN QUANTUM MECHANICS 26

This is clearly a discrete transformation. Application of parity twice returns

the initial state implying that P̂ 2 = 1. Therefore, the eigenvalues of the parity
operation (if such exist) are ±1. A wavefunction will have a defined parity
if and only if it is an even or odd function. For example, for ψ(x) = cos(x),
P̂ ψ = cos(−x) = cos(x) = ψ; thus ψ is even and P = 1. Similarly ψ =
sin(x) is odd with P = −1. Later, in the next chapter, we will encounter the
spherical harmonic functions which have the following important symmetry
under parity, P̂ Y!m = (−1)! Ylm . Parity will be conserved if the Hamiltonian
is invariant under the parity operation, i.e. if the Hamiltonian is invariant
under a reversal of sign of all the coordinates.5
In classical mechanics, the time-reversal operation involves simply “run-
ning the movie backwards”. The time-reversed state of the phase space
coordinates (x(t), p(t)) is defined by (xT (t), pT (t)) where xT (t) = x(t) and
pT (t) = −p(t). Hence, if the system evolved from (x(0), p(0)) to (x(t), p(t)) in
time t and at t we reverse the velocity, p(t) → −p(t) with x(t) → x(t), at time
2t the system would have returned to x(2t) = x(0) while p(2t) = −p(0). If this
happens, we say that the system is time-reversal invariant. Of course, this is
just the statement that Newton’s laws are the same if t → −t. A notable case
where this is not true is that of a charged particle in a magnetic field.
As with classical mechanics, time-reversal in quantum mechanics involves
the operation t → −t. However, referring to the time-dependent Schrödinger
equation, i!∂t ψ(x, t) = Ĥψ(x, t), we can see that the operation t → −t is
equivalent to complex conjugation of the wavefunction, ψ → ψ ∗ if Ĥ ∗ = Ĥ.
Let us then consider the time-evolution of ψ(x, t),
i c.c. i ∗ (x)t evolve i i ∗ (x)t
ψ(x, 0) → e− ! Ĥ(x)t ψ(x, 0) → e+ ! Ĥ ψ ∗ (x, 0) → e− ! Ĥ(x)t e+ ! Ĥ ψ ∗ (x, 0) .

If we require that ψ(x, 2t) = ψ ∗ (x, 0), we must have Ĥ ∗ (x) = Ĥ(x). Therefore,
Ĥ is invariant under time-reversal if and only if Ĥ is real.

' Info. Although the group of space-transformations covers the symmetries

that pertain to “low-energy” quantum physics, such as atomic physics, quantum op-
tics, and quantum chemistry, in nuclear physics and elementary particle physics new
observables come into play (e.g. the isospin quantum numbers and the other quark
charges in the standard model). They generate symmetry groups which lack a classical
counterpart, and they do not have any obvious relation with space-time transforma-
tions. These symmetries are often called internal symmetries in order to underline
this fact.

3.2.2 Consequences of symmetries: multiplets

Having established how to identify whether an operator belongs to a group
of symmetry transformations, we now consider the consequences. Consider
a single unitary transformation Û in the Hilbert space, and an observable Â
which commutes with Û , [Û , Â] = 0. If  has an eigenvector |a", it follows
that Û |a" will be an eigenvector with the same eigenvalue, i.e.

Û Â|a" = ÂU |a" = aU |a" .

This means that either:

5
In high energy physics, parity is a symmetry of the strong and electromagnetic forces, but
does not hold for the weak force. Therefore, parity is conserved in strong and electromagnetic
interactions, but is violated in weak interactions.

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3.3. THE HEISENBERG PICTURE 27

1. |a" is an eigenvector of both  and Û , or

2. the eigenvalue a is degenerate: the linear space spanned by the vectors

Û n |a" (n integer) are eigenvectors with the same eigenvalue.

This mathematical argument leads to the conclusion that, given a group G of

unitary operators Û (x), x ∈ G, for any observable which is invariant under
these transformations, i.e.

[Û (x), Â] = 0 ∀x ∈ G ,

its discrete eigenvalues and eigenvectors will show a characteristic multiplet

structure: there will be a degeneracy due to the symmetry such that the
eigenvectors belonging to each eigenvalue form an invariant subspace under
the group of transformations.

' Example: For example, if the Hamiltonian commutes with the angular mo-
mentum operators, L̂i , i = x, y, z, i.e. it is invariant under three-dimensional rota-
tions, an energy level with a given orbital quantum number , is at least (2, + 1)-fold
degenerate. Such a degeneracy can be seen as the result of non-trivial actions of
the operator L̂x and L̂y on an energy (and L̂z ) eigenstate |E, ,, m" (where m is the
magnetic quantum number asssociated with L̂z ).

3.3 The Heisenberg Picture

Until now, the time dependence of an evolving quantum system has been
placed within the wavefunction while the operators have remained constant –
this is the Schrödinger picture or representation. However, it is some-
times useful to transfer the time-dependence to the operators. To see how, let
us consider the expectation value of some operator B̂,

#ψ(t)|B̂|ψ(t)" = #e−iĤt/!ψ(0)|B̂|e−iĤt/!ψ(0)" = #ψ(0)|eiĤt/!B̂e−iĤt/!|ψ(0)" .

According to rules of associativity, we can multiply operators together be-

fore using them. If we define the operator B̂(t) = eiĤt/!B̂e−iĤt/!, the time-
dependence of the expectation values has been transferred from the wavefunc- Werner Heisenberg 1901-76
A German physi-
tion. This is called the Heisenberg picture or representation and in it, cist and one of
the operators evolve with time while the wavefunctions remain constant. In the founders of
the quantum the-
this representation, the time derivative of the operator itself is given by ory, he is best
known for his un-
iĤ iĤt/! −iĤt/! iĤ −iĤt/! certainty princi-
∂t B̂(t) = e B̂e − eiĤt/!B̂ e ple which states
! ! that it is impossi-
i i ble to determine
= eiĤt/![Ĥ, B̂]e−iĤt/! = [Ĥ, B̂(t)] . with arbitrarily high accuracy both
! ! the position and momentum of a par-
ticle. In 1926, Heisenberg devel-
oped a form of the quantum theory
p̂2
' Exercise. For the general Hamiltonian Ĥ = + V (x), show that the posi-
2m
known as matrix mechanics, which
was quickly shown to be fully equiva-
tion and momentum operators obey Hamilton’s classical equation of motion. lent to Erwin Schrödinger’s wave me-
chanics. His 1932 Nobel Prize in
Physics cited not only his work on
quantum theory but also work in nu-
clear physics in which he predicted
3.4 Quantum harmonic oscillator the subsequently verified existence of
two allotropic forms of molecular hy-
As we will see time and again in this course, the harmonic oscillator assumes a drogen, differing in their values of nu-
clear spin.
priveledged position in quantum mechanics and quantum field theory finding

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3.4. QUANTUM HARMONIC OSCILLATOR 28

numerous and somtimes unexpected applications. It is useful to us now in

that it provides a platform for us to implement some of the technology that
has been developed in this chapter. In the one-dimensional case, the quantum
harmonic oscillator Hamiltonian takes the form,
p̂2 1
Ĥ = + mω 2 x2 ,
2m 2
where p̂ = −i!∂x . To find the eigenstates of the Hamiltonian, we could
look for solutions of the linear second order differential equation correspond-
ing to the time-independent Schrödinger equation, Ĥψ = Eψ, where Ĥ =
!2 2
− 2m ∂x + 21 mω 2 x2 . The integrability of the Schrödinger operator in this case
allows the stationary states to be expressed in terms of a set of orthogonal
functions known as Hermite polynomials. However, the complexity of the ex-
act eigenstates obscure a number of special and useful features of the harmonic
oscillator system. To identify these features, we will instead follow a method
based on an operator formalism.
The form of the Hamiltonian as the sum of the squares of momenta and First few states of the quantum
position suggests that it can be recast as the “square of an operator”. To this harmonic oscillator. Not that the
end, let us introduce the operator parity of the state changes from
2 2 even to odd through consecutive
3 4 3 4
mω p̂ † mω p̂ states.
a= x+i , a = x−i ,
2! mω 2! mω
where, for notational convenience, we have not drawn hats on the operators a
and its Hermitian conjuate a† . Making use of the identity,
mω 2 p̂ i Ĥ 1
a† a = x + + [x, p̂] = −
2! 2!mω 2! !ω 2
and the parallel relation, aa† = Ĥ
!ω + 12 , we see that the operators fulfil the
commutation relations
[a, a† ] ≡ aa† − a† a = 1 .

Then, setting n̂ = a† a, the Hamiltonian can be cast in the form

Ĥ = !ω(n̂ + 1/2) .

Since the operator n̂ = a† a must lead to a positive definite result, we see

that the eigenstates of the harmonic oscillator must have energies of !ω/2 or
higher. Moreover, the ground state |0" can be identified by finding the state
for which a|0" = 0. Expressed in the coordinate basis, this translates to the
equation,6
3 4 2
! mω −mωx2 /2!
x+ ∂x ψ0 (x) = 0, ψ0 (x) = #x|0" = e .
mω π 1/2 !
Since n̂|0" = a† a|0" = 0, this state is an eigenstate with energy !ω/2. The
higher lying states can be found by acting upon this state with the operator
a† . The proof runs as follows: If n̂|n" = n|n", we have
n̂(a† |n") = a† ()*+
aa† |n" = (a† ()*+
a† a +a† )|n" = (n + 1)a† |n"
a† a+1 n̂
!
6
Formally, in coordinate basis, we have #x" |a|x! "
R = δ(x − x)(a + mω ∂x ) and #x|0! = ψ0 (x).
Then making use of the resolution of identity dx|x!#x| = I, we have
Z „ «
!
#x|a|0! = 0 = dx #x|a|x" !#x" |0! = x + ∂x ψ0 (x) .
mω

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3.4. QUANTUM HARMONIC OSCILLATOR 29

or, equivalently, [n̂, a† ] = a† . In other words, if |n" is an eigenstate of n̂ with

eigenvalue n, then a† |n" is an eigenstate with eigenvalue n + 1.
From this result, we can deduce that the eigenstates for a “tower” |0",
|1" = C1 a† |0", |2" = C2 (a† )2 |0", etc., where Cn denotes the normalization. If
#n|n" = 1 we have

#n|aa† |n" = #n|(n̂ + 1)|n" = (n + 1) .

Therefore, with |n + 1" = √n+11

a† |n" the state |n + 1" is also normalized,
#n + 1|n + 1" = 1. By induction, we can deduce the general normalization,

1
|n" = √ (a† )n |0" ,
n!

with #n|n% " = δnn" , Ĥ|n" = !ω(n + 1/2)|n" and

√ √
a† |n" = n + 1|n + 1", a|n" = n|n − 1" .

The operators a and a† represent ladder operators and have the effect of
lowering or raising the energy of the state.
In fact, the operator representation achieves something quite remarkable
and, as we will see, unexpectedly profound. The quantum harmonic oscillator
describes the motion of a single particle in a one-dimensional potential well.
It’s eigenvalues turn out to be equally spaced – a ladder of eigenvalues, sepa-
rated by a constant energy !ω. If we are energetic, we can of course translate
our results into a coordinate representation ψn (x) = #x|n".7 However, the
operator representation affords a second interpretation, one that lends itself
to further generalization in quantum field theory. We can instead interpret
the quantum harmonic oscillator as a simple system involving many fictitious
particles, each of energy !ω. In this representation, known as the Fock space,
the vacuum state |0" is one involving no particles, |1" involves a single particle,
|2" has two and so on. These fictitious particles are created and annihilated
by the action of the raising and lowering operators, a† and a with canoni-
cal commutation relations, [a, a† ] = 1. Later in the course, we will find that
these commutation relations are the hallmark of bosonic quantum particles
and this representation, known as the second quantization underpins the
quantum field theory of the electromagnetic field.

' Info. There is evidently a huge difference between a stationary (Fock) state
of the harmonic oscillator and its classical counterpart. For the classical system, the
equations of motion are described by Hamilton’s equations of motion,
P
Ẋ = ∂P H = , Ṗ = −∂X H = −∂x U = −mω 2 X ,
m
where we have used capital letters to distinguish them from the arguments used to de-
scribe the quantum system. In the phase space, {X(t), P (t)}, these equations describe
a clockwise rotation along an elliptic trajectory specified by the initial conditions
{X(0), P (0)}. (Normalization of momentum by mω makes the trajectory circular.)
7
Expressed in real space, the harmonic oscillator wavefunctions are in fact described by
the Hermite polynomials,
r „r « » –
1 mω mωx2
ψn (x) = #x|n! = H n x exp − ,
2n n! ! 2!
2
dn −x2
where Hn (x) = (−1)n ex dxn
e .

Advanced Quantum Physics

3.4. QUANTUM HARMONIC OSCILLATOR 30

On the other hand, the time dependence of the Fock space state, as of any sta-
tionary state, is exponential,

ψn (x, t) = #x|n"e−iEn t/! ,

and, as a result, gives time-independent expectation values of x, p, or any function

thereof. The best classical image for such a state on the phase plane is a circle of
radius r = x0 (2n + 1)1/2 , where x0 = (!/mω)1/2 , along which the wavefunction is
uniformly spread as a standing wave.
It is natural to ask how to form a wavepacket whose properties would be closer to
the classical trajectories. Such states, with the centre in the classical point {X(t), P (t)},
and the smallest possible product of quantum uncertainties of coordinate and momen-
tum, are called Glauber states.8 Conceptually the simplest way to present the
Glauber state |α" is as the Fock ground state |0" with the centre shifted from the
origin to the classical point {X(t), P (t)}. (After such a shift, the state automati-
cally rotates, following the classical motion.) Let us study how this shift may be
implemented in quantum mechanics. The mechanism for such shifts are called the
translation operators.
Previously, we have seen that the space and momentum translation operators are
given by
# $ # $
i i
F̂X = exp − p̂X , F̂P = exp − P x̂ .
! !
A shift by both X and P is then given by
# $
i † ∗ ∗
a−αa†
F̂α = exp (P x̂ − p̂X) = eαa −α a , F̂α† = eα ,
!

where α is the (normalised) complex amplitude of the classical oscillations we are

trying to approximate, i.e. α = √2x
1
(X + i mω
P
). The Glauber state is then defined
0

by |α" = F̂α |0".

Working directly with the shift operator is not too convenient because of its
exponential form. However, it turns out that a much simpler representation for the
Glauber state is possible. To see this, let us start with the following general property
of exponential operators: if [Â, B̂] = µ (where  and B̂ are operators, and µ is a
c-number), then (exercise – cf. Eq. (3.3)),

e B̂e− = B̂ + µ . (3.4)

If we define  = α∗ a − αa† , then F̂α = e− and F̂α† = e . If we then take B̂ = I, we
have µ = 0, and F̂α† F̂α = I. This merely means that the shift operator is unitary -
not a big surprise, because if we shift the phase point by (+α) and then by (−α), we
certainly come back to the initial position.
If we take B̂ = a, using the commutation relations,

[Â, B̂] = [α∗ a − αa† , a] = −α[a† , a] = α ,

so that µ = α, and F̂α† aF̂α = a + α. Now let us consider the operator F̂α F̂α† aF̂α .
From the unitarity condition, this must equal aF̂α , while application of Eq. (3.4)
yields F̂α a + αF̂α , i.e.

aF̂α = F̂α a + αF̂α .

Applying this equality to the ground state |0" and using the following identities,
a|0" = 0 and F̂α |0" = |α", we finally get a very simple and elegant result:

a|α" = α|α" .

8
After R. J. Glauber who studied these states in detail in the mid-1960s, though they
were known to E. Schrödinger as early as in 1928. Another popular name, coherent states,
does not make much sense, because all the quantum states we have studied so far (including
the Fock states) may be presented as coherent superpositions.

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3.5. POSTULATES OF QUANTUM THEORY 31

Thus the Glauber state is an eigenstate of the annihilation operator, corresponding to

the eigenvalue α, i.e. to the (normalized) complex amplitude of the classical process
approximated by the state. This fact makes the calculations of the Glauber state
properties much simpler.
Presented as a superposition of Fock states, the Glauber state takes the form
(exercise – try making use of the BCH identity (3.3).)
∞
& 2 αn
|α" = αn |n", αn = e−|α| /2
.
n=0
(n!)1/2

This means that the probability of finding the system in level n is given by the
Poisson distribution, Pn = |αn |2 = #n"n e−%n& /n! where #n" = |α|2 . More importantly,
δn = #n"1/2 / #n" when #n" 0 1 – the Poisson distribution approaches the Gaussian
distribution when #n" is large.
The time-evolution of Glauber states may be described most easily in the Schrödinger
representation when the time-dependence is transferred to the wavefunction. In this
case, α(t) ≡ √2x1
(X(t) + i Pmω
(t)
), where {X(t), P (t)} is the solution to the classical
0
equations of motion, α̇(t) = −iωα(t). From the solution, α(t) = α(0)e−iωt , one may
show that the average position and momentum evolve classically while their fluctua-
tions remain stationary,
3 41/2 3 41/2
x0 ! mωx0 !mω
∆x = √ = , ∆p = √ = .
2 2mω 2 2m
In the quantum theory of measurements these expressions are known as the “standard
quantum limit”. Notice that their product ∆x ∆p = !/2 corresponds to the lower
bound of the Heisenberg’s uncertainty relation.

' Exercise. Show that, in position space, the Glauber state takes the form
# $
mω Px
#x|α" = ψα (x) = C exp − (x − X)2 + i .
2! !

This completes our abridged survey of operator methods in quantum me-

chanics. With this background, we are now in a position to summarize the
basic postulates of quantum mechanics.

3.5 Postulates of quantum theory

Since there remains no “first principles” derivation of the quantum mechanical
equations of motion, the theory is underpinned by a set of “postulates” whose
validity rest on experimental verification. Needless to say, quantum mechanics
remains perhaps the most successful theory in physics.
' Postulate 1. The state of a quantum mechanical system is completely
specified by a function Ψ(r, t) that depends upon the coordinates of the
particle(s) and on time. This function, called the wavefunction or state
function, has the important property that |Ψ(r, t)|2 dr represents the
probability that the particle lies in the volume element dr ≡ dd r located
at position r at time t.
The wavefunction must satisfy certain mathematical conditions because
of this probabilistic interpretation. For the case of a single particle, the
net probability of finding it at some
' ∞ point in space must be unity leading
to the normalization condition, −∞ |Ψ(r, t)|2 dr = 1. It is customary to
also normalize many-particle wavefunctions to unity. The wavefunction
must also be single-valued, continuous, and finite.

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3.5. POSTULATES OF QUANTUM THEORY 32

' Postulate 2. To every observable in classical mechanics there corre-

sponds a linear, Hermitian operator in quantum mechanics.
If we require that the expectation value of an operator  is real, then
it follows that  must be a Hermitian operator. If the result of a mea-
surement of an operator  is the number a, then a must be one of the
eigenvalues, ÂΨ = aΨ, where Ψ is the corresponding eigenfunction. This
postulate captures a central point of quantum mechanics – the values
of dynamical variables can be quantized (although it is still possible to
have a continuum of eigenvalues in the case of unbound states).

' Postulate 3. If a system is in a state described by a normalized wave-

function Ψ, then the average value of the observable corresponding to Â
is given by
! ∞
#A" = Ψ∗ ÂΨdr .
−∞

If the system is in an eigenstate of  with eigenvalue a, then any mea-

surement of the quantity A will yield a. Although measurements must
always yield an eigenvalue, the state does not have to be an eigenstate
of  initially. An arbitrary state can be expanded
% in the complete set
of eigenvectors of  ( ÂΨi = ai Ψi ) as Ψ = ni ci Ψi , where n may go to
infinity. In this case, the probability of obtaining the result ai from the
measurement of  is given by P (ai ) = |#Ψi |Ψ"|2 = |ci |2 . The expecta-
tion value of  for the state Ψ is the sum over all possible values of the
measurement and given by
& &
#A" = ai |#Ψi |Ψ"|2 = ai |ci |2 .
i i

Finally, a measurement of Ψ which leads to the eigenvalue ai , causes the

wavefunction to “collapses” into the corresponding eigenstate Ψi . (In
the case that ai is degenerate, then Ψ becomes the projection of Ψ onto
the degenerate subspace). Thus, measurement affects the state of the
system.

' Postulate 4. The wavefunction or state function of a system evolves in

time according to the time-dependent Schrödinger equation
∂Ψ
i! = ĤΨ(r, t) ,
∂t

where Ĥ is the Hamiltonian of the system. If Ψ is an eigenstate of Ĥ,

it follows that Ψ(r, t) = Ψ(r, 0)e−iEt/!.

Advanced Quantum Physics

Chapter 4

Quantum mechanics in more

than one-dimension

Previously, we have explored the manifestations of quantum mechanics in one

spatial dimension and discussed the properties of bound and unbound states.
The concepts developed there apply equally to higher dimension. However,
for a general two or three-dimensional potential, without any symmetry, the
solutions of the Schrödinger equation are often inaccessible. In such situations,
we may develop approximation methods to address the properties of the states
(see chapter 7). However, in systems where there is a high degree of symmetry,
the quantum mechanics of the system can often be reduced to a tractable low-
dimensional theory.

4.1 Rigid diatomic molecule

As a pilot example let us consider the quantum mechanics of a rigid diatomic
molecule with nuclear masses m1 and m2 , and (equilibrium) bond length, Re
(see figure). Since the molecule is rigid, its coordinates can be specified by
its centre of mass, R = m1mr11 +m
+m2 , and internal orientation, r = r2 − r1
2 r2

(with |r| = Re ). Defining the total mass M = m1 + m2 , and moment of

inertia, I = µRe2 , where µ = m1 m2 /(m1 + m2 ) denotes the reduced mass,
the corresponding Hamiltonian can be then separated into the kinetic energy
associated with the centre of mass motion and the rotational kinetic energy,

P̂2 L̂2
Ĥ = + , (4.1)
2M 2I

where P̂ = −i!∇R and L̂ = r × p̂ denotes the angular momentum associated

with the internal degrees of freedom. Since the internal and centre of mass
degrees of freedom separate, the wavefunction can be factorized as ψ(r, R) =
eiK·R Y (r), where the first factor accounts for the free particle motion of the
body, and the second factor relates to the internal angular degrees of freedom.
As a result of the coordinate separation, we have reduced the problem
of the rigid diatomic molecule to the study of the quantum mechanics of a
particle moving on a sphere – the rigid rotor,

L̂2
Ĥrot = .
2I
The eigenstates of this component of the Hamiltonian are simply the states of
the angular momentum operator. Indeed, in any quantum mechanical system
involving a radial potential, the angular momentum will be conserved, i.e.

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4.2. ANGULAR MOMENTUM 34

[Ĥ, L̂] = 0 meaning that the angular component of the wavefunction can be
indexed by the states of the angular momentum operator. We therefore now
digress to discuss the quantum mechanics of angular momentum.

4.2 Angular momentum

4.2.1 Commutation relations
Following the usual canonical quantization procedure, the angular momentum
operator is defined by L̂ = r×p̂ where, as usual, r and p̂ obey the commutation
relations, [p̂i , rj ] = −i!δij .1 Using this relation, one may then show that
the angular momentum operators obey the spin commutation relations,
(exercise)

[L̂i , L̂j ] = i!#ijk L̂k . (4.2)

where, as usual, #ijk denotes the totally antisymmetric tensor — the Levi-
Civita symbol.2

$ Exercise. Show that the angular momentum operator commutes with the
p̂2
Hamiltonian of a particle moving in a central potential, Ĥ = 2m + V (r). Show that
the Hamiltonian of a free particle of mass m confined to a sphere of radius R is given
L̂2
by Ĥ = 2mR 2.

4.2.2 Eigenvalues of angular momentum

In the following, we will construct a basis set of angular momentum states.
Since the angular momentum is a vector quantity, it may be characterized
by its magnitude and direction. For the former, let us define the operator
L̂2 = L̂2x + L̂2y + L̂2z . With the latter, since the separate components of the
angular momentum are all mutually non-commuting, we cannot construct a
common set of eigenstates for any two of them. They do, however, commute
with L̂2 (exercise). Therefore, in the following, we will look for an eigenbasis
of L̂2 and one direction, say L̂z ,
L̂2 |a, b$ = a|a, b$, L̂z |a, b$ = b|a, b$ .
To find |a, b$, we could simply proceed by looking for a suitable coordinate
basis to represent L̂2 and L̂z in terms of differential operators. However,
although we will undertake such a programme in due course, before getting
to this formalism, we can make substantial progress without resorting to an
explicit coordinate representation.

$ Info. Raising and lowering operators for angular momentum: The set
of eigenvalues a and b can be obtained by making use of a trick based on a “ladder
operator” formalism which parallels that used in the study of the quantum harmonic
oscillator in section 3.4. Specifically, let us define the raising and lowering operators,

L̂± = L̂x ± iL̂y .

1
In this chapter, we will index the angular momentum operators with a ‘hat’. Later, we
will become lazy and the hat may well disappear.
2
Recall that !ijk = 1 if (i, j, k) is an even permutation of (1,2,3), −1 if it is an odd
permutation, and 0 if any index is repeated.

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4.2. ANGULAR MOMENTUM 35

With this definition, one may then show that (exercise)

[L̂z , L̂± ] = ±!L̂± .

Since each component of the angular momentum commutes with L̂2 , we can deduce
that the action of L̂± on |a, b$ cannot affect the value of a relating to the magnitude
of the angular momentum. However, they do effect the projection:
L̂z L̂± |a, b$ = L̂± L̂z |a, b$ + [L̂z , L̂± ]|a, b$ = (b ± !)L̂± |a, b$ .
Therefore, if |a, b$ is an eigenstate of L̂z with eigenvalue b, L̂± |a, b$ is either zero,
or an eigenstate of L̂z with eigenvalue b ± !, i.e. L̂± |a, b$ = C± (a, b)|a, b ± !$ where
C± (a, b) is a normalisation constant.
To fix the normalisation, we may note that the norm,
!! !!2
!! !! †
!!L̂± |a, b$!! = %a, b|L̂± L̂± |a, b$ = %a, b|L̂∓ L̂± |a, b$ ,

where we have used the identity L̂†± = L̂∓ . Then, making use of the relation L̂∓ L̂± =
L̂2x + L̂2y ± i[L̂x L̂y ] = L̂2 − L̂2z ± !L̂z , and the presumed normalisation, %a, b|a, b$ = 1,
one finds
!! !!2 " #
!! !!
!!L̂± |a, b$!! = %a, b| L̂2 − L̂2z ± !L̂z |a, b$ = a − b2 ∓ !b . (4.3)

As a represents the eigenvalue of a sum of squares of Hermitian operators, it is

necessarily non-negative. Moreover, b is real. Therefore, for a given a, b must be
bounded: there must be a bmax and a (negative or zero) bmin . In particular,
!! !!2
!! !!
!!L̂+ |a, bmax $!! = a − b2max − !bmax
!! !!2
!! !!
!!L̂− |a, bmin $!! = a − b2min + !bmin ,

For a given a, bmax and bmin are determined uniquely — there cannot be two states
with the same a but different b annihilated by L̂+ . It also follows immediately that
a = bmax (bmax +!) and bmin = −bmax . Furthermore, we know that if we keep operating
on |a, bmin $ with L̂+ , we generate a sequence of states with L̂z eigenvalues bmin + !,
bmin + 2!, bmin + 3!, · · ·. This series must terminate, and the only possible way for
that to happen is for bmax to be equal to bmin + n! with n integer, from which it
follows that bmax is either an integer or half an odd integer times !
At this point, we switch to the standard notation. We have established that the
eigenvalues of L̂z form a finite ladder, with spacing !. We write them as m!, and %
is used to denote the maximum value of m, so the eigenvalue of L̂2 , a = %(% + 1)!2 .
Both % and m will be integers or half odd integers, but the spacing of the ladder of
m values is always unity. Although we have been writing |a, b$ with a = %(% + 1)!2 ,
b = m! we shall henceforth follow convention and write |%, m$.

In summary, the operators L̂2 and L̂z have a common set of orthonormal
eigenstates |%, m$ with Figure 4.1: The following is a
schematic showing the angular
momentum $ scheme for % = √ 2
L̂2 |%, m$ = %(% + 1)!2 |%, m$, L̂z |%, m$ = m!|%, m$ , (4.4) with L2 = 2(2 + 1)! = 6!
and the five possible values for
the Lz projection.
where %, m are integers or half-integers. The allowed quantum numbers m
form a ladder with step spacing unity, the maximum value of m is %, and
the minimum value is −%. With these results, we may then return to the
normalization of the raising and lowering operators. In particular, making use
of Eq. (4.3), we have
$
L̂+ |%, m$ = $%(% + 1) − m(m + 1)!|l, m + 1$
. (4.5)
L̂− |%, m$ = %(% + 1) − m(m − 1)!|l, m − 1$

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4.2. ANGULAR MOMENTUM 36

The use of m to denote the component of angular momentum in one direc-

tion came about because a Bohr-type electron in orbit is a current loop, with
a magnetic moment parallel to its angular momentum. So the m measured
the component of magnetic moment in a chosen direction, usually along an
external magnetic field. For this reason, m is often termed the magnetic
quantum number.

4.2.3 Representation of the angular momentum states

Having established expressions for the eigenvalues of the angular momentum
operators, it is now necessary to establish coordinate representations for the
corresponding eigenstates, Y!m (θ, φ) = %θ, φ|%, m$. Here the angles θ and φ
denote the spherical coordinates parameterising the unit sphere (see figure).
Previously, we obtained the eigenvalues of the angular momentum operator by
making use of the raising and lowering operators in a manner that parallelled
the study of the quantum harmonic oscillator. Similarly, to obtain explicit
expressions for the eigenstates, we must make use of the coordinate represen-
tation of these operators. With r = rêr , the gradient operator can be written
in spherical polar coordinates as
1 1
∇ = êr ∂r + êθ ∂θ + êφ ∂φ .
r r sin θ
From this result, we thus obtain

L̂z = −i!∂φ , L̂± = !e±iφ (±∂θ + i cot θ∂φ ) , (4.6)

and, at least formally,

% &
1 1
L̂ = −!
2 2
∂θ (sin θ∂θ ) + 2
∂ .
sin θ sin2 θ φ

Beginning with the eigenstates of L̂z , the eigenvalue equation (4.4), and
making use of the expression above, we have

−i!∂φ Y!m (θ, φ) = m!Y!m (θ, φ) .

Since the left hand side depends only on φ, the solution is separable and takes
the form Y!m (θ, φ) = F (θ)eimφ . Note that, since m is integer, the continuity
of the wavefunction, Y!m (θ, φ + 2π) = Y!m (θ, φ), is ensured.
To determine the second component of the eigenstates, F (θ), we could
immediately turn to the eigenvalue equation involving the differential operator
for L̂2 ,
% &
1 m2 2
∂θ (sin θ∂θ ) − ∂ F (θ) = %(% + 1)F (θ) .
sin θ sin2 θ φ
However, to construct the states, it is easier to draw upon the properties of
the angular momentum raising and lowering operators (much in the same way
that the Hermite polynomials are generated by the action of ladder operators
in the harmonic oscillator problem).
Consider then the state of maximal m, |%, %$, for which L̂+ |%, %$ = 0. Mak-
ing use of the coordinate representation of the raising operator above together
with the separability of the wavefunction, this relation implies that

0 = %θ, φ|L̂+ |%, %$ = !eiφ (∂θ + i cot θ∂φ ) Y!! (θ, φ) = !ei(!+1)φ (∂θ − % cot θ) F (θ) .

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4.2. ANGULAR MOMENTUM 37

From this result it follows that ∂θ F (θ) = % cot θF (θ) with the solution F (θ) =
C sin! θ, and C a constant of normalization. States with values of m lower
than % can then be obtained simply by repeated application of the angular
momentum lowering operator L̂− to the state |%, %$. This amounts to the
relation
' (
Y!m (θ, φ) = C(L̂− )!−m sin! θei!φ
' (
= C (−∂θ + i cot θ∂φ )!−m sin! θei!φ .

The eigenfunctions produced by this procedure are well known and referred
to as the spherical harmonics. In particular, one finds that the normalized
eigenstates take the form,
% &1/2
2% + 1 (% − |m|)! |m|
Y!m (θ, φ) = (−1) m+|m|
P! (cos θ)eimφ , (4.7)
4π (% + |m|)!

where
(1 − ξ 2 )m/2 dm+! 2
P!m (ξ) = (ξ − 1)! ,
2! %! dξ m+!
represent the associated Legendre polynomials. In particular, for the first
few angular momentum states, we have

Y00 = √1
)4π )
Y10 = 3
cos θ, Y11 = − 8π e sin θ
3 iφ
) 4π ) )
Y20 = 5
16π (3 cos 2 θ − 1), Y
21 = − 15 iφ
8π e sin θ cos θ, Y22 = 15 2iφ
32π e sin2 θ

Figure 4.2 shows a graphical representation of the states for the lowest spher-
ical harmonics. From the colour coding of the states, the symmetry, Y!,−m =
(−1)m Y!m∗ is manifest.

As a complete basis set, the spherical harmonics can be used as a resolution

of the identity
∞ *
* !
|%, m$%%, m| = I .
!=0 m=−!

Equivalently, expressed in the coordinate basis, we have

∞ *
* !
∗ 1
Y!,m (θ% , φ% )Y!,m (θ, φ) = δ(θ − θ% )δ(φ − φ% ) ,
sin θ
!=0 m=−!

where the prefactor sin θ derives from the measure. Similarly, we have the
orthogonality condition,
+ π + 2π
∗
dθ sin θ Y!,m (θ, φ)Y!! ,m! (θ, φ) = δ!!! δmm! .
0 0

After this lengthy digression, we may now return to the problem of the
quantum mechanical rotor Hamiltonian and the rigid diatomic molecule. From
the analysis above, we have found that the eigenstates of the Hamiltonian (4.1)
are given by ψ(R, r) = √12π eiK·R Y!,m (θ, φ) with eigenvalues

!2 K2 !2
EK,! = + %(% + 1) ,
2M 2I

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4.3. THE CENTRAL POTENTIAL 38

Figure 4.2: First four groups of spherical harmonics, Y!m (θ, φ) shown as a function
of spherical angular coordinates. Specifically, the plots show the surface generated by
|Re Y!m (θ, φ)| to fix the radial coordinate and the colours indicate the relative sign of
the real part.

where each K, % value has a 2% + 1-fold degeneracy.

$ Exercise. Using this result, determine the dependence of the heat capacity
of a gas of rigid diatomic molcules on the angular degrees of freedom. How would
this result change if the diatomic gas was constrained to just two spatial dimensions,
i.e. the axis of rotation was always perpendicular to the plane in which the molecules
can move?

4.3 The central potential

In a system where the central force field is entirely radial, the potential energy
depends only on r ≡ |r|. In this case, a general non-relativistic Hamiltonian
for a single particle is given by

p̂2
Ĥ = + V (r) .
2m
In the classical system, L2 = (r × p)2 = r2 p2 − (r · p)2 . As a result, we can
2
set p2 = Lr2 + p2r , where pr ≡ er · p denotes the radial component of the
momentum. In the quantum system, since the space and position coordinates
do not commute, we have (exercise)

L̂2 = r2 p̂2 − (r · p̂)2 + i!r · p̂ .

In spherical coordinates, since r · p̂ = −i!r · ∇ = −i!r∂r , it follows that

p̂2 = L̂r2 − !r2 [(r∂r )2 + r∂r ]. Equivalently, noting that (r∂r )2 + r∂r = ∂r2 + 2r ∂r ,
2 2

we can set
% &
L̂2 2
p̂ = 2 − ! ∂r + ∂r .
2 2 2
r r

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4.4. ATOMIC HYDROGEN 39

Finally, substituted into the Schrödinger equation, we obtain the eigenvalue

equation
, - . /
!2 2 L̂2
− ∂r2 + ∂r + + V (r) ψ(r) = Eψ(r) . (4.8)
2m r 2mr2

Since we already know the eigenstates of L̂2 , we can immediately take ad-
vantage of the separability of the Hamiltonian to find that ψ(r) = R(r)Y!,m (θ, φ),
where the radial part of the wavefunction is set by
% - . &
!2 2 !2
− ∂r + ∂r +
2
%(% + 1) + V (r) R(r) = ER(r) .
2m r 2mr2
Finally, we can further simplify this expression by setting R(r) = u(r)/r,
whereupon we obtain the “one-dimensional” equation
% 2 2 &
! ∂r
− + Veff (r) u(r) = u(r) , (4.9)
2m
! 2
where the effective potential, Veff (r) = 2mr 2 %(% + 1) + V (r), acquires an ad-
ditional component due to the centrifugal component of the force. Here the
equation must be solved subject to the boundary condition u(0) = 0. From
the normalization condition,
+ + ∞
1
d r |ψ(r)| =
3 2
drr2 2 |u(r)|2 = 1 ,
0 r

for a bound state to exist, limr→∞ |u(r)| ≤ a/r1/2+% with # > 0.

From this one-dimensional form of the Hamiltonian, the question of the
existence of bound states in higher dimension becomes clear. Since the wave-
function u(r) vanishes at the origin, we may map the Hamiltonian from the
half-line to the full line with the condition that we admit only antisymmetric
wavefunctions. The question of bound states can then be related back to the
one-dimensional case. Previously, we have seen that a symmetric attractive
potential always leads to a bound state in one-dimension. However, odd parity
states become bound only at a critical strength of the interaction.

4.4 Atomic hydrogen

The Hydrogen atom consists of an electron bound to a proton by the Coulomb
potential,
1 e2
V (r) = − .
4π#0 r
We can generalize the potential to a nucleus of charge Ze without complica-
tion of the problem. Since we are interested in finding bound states of the
proton-electron system, we are looking for solutions with E negative. At large
separations, the wave equation (4.9) simplifies to

!2 ∂r2
− u(r) * Eu(r) ,
2m
√
having approximate solutions eκr and e−κr , where !κ = −2mE. (Here,
strictly speaking, m should denote the reduced mass of electron-proton sys-
tem.) The bound states we are looking for, of course, have exponentially
decreasing wavefunctions at large distances.

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4.4. ATOMIC HYDROGEN 40

To further simplify the wave equation, it is convenient to introduce the

dimensionless variable ρ = κr, leading to the equation
- .
2ν %(% + 1)
∂ρ u(ρ) = 1 −
2
+ u(ρ) ,
ρ ρ2

where (for reasons which will become apparent shortly) we have introduced
Ze2 κ
the dimensionless parameter ν = 4π% 0 2E
. Notice that in transforming from r
to the dimensionless variable ρ, the scaling factor depends on energy, so will
be different for different energy bound states! Consider now the behaviour of
the wavefunction near the origin. The dominant term for sufficiently small ρ
is the centrifugal component, so

%(% + 1)
∂ρ2 u(ρ) * u(ρ) ,
ρ2

for which the solutions are u(ρ) ∼ ρ−! and u(ρ) ∼ ρ!+1 . Since the wavefunction
cannot be singular, we must choose the second solution.
We have established that the wavefunction decays as e−κr = e−ρ at large
distances, and goes as ρ!+1 close to the origin. Factoring out these two asymp-
totic behaviours, let us then define w(ρ) such that u(ρ) = e−ρ ρ!+1 w(ρ). We
leave it as a tedious but straightforward exercise to show that

ρ∂ρ2 w(ρ) + 2(% + 1 − ρ)∂ρ w(ρ) + 2(ν − (% + 1))w(ρ) = 0 .

0∞
Substituting the trial series solution, w(ρ) = k=0 wk ρ ,
k we obtain a recur-
rence relation between successive coefficients:
wk+1 2(k + % + 1 − ν)
= .
wk (k + 1)(k + 2(% + 1))

For large values of k, wk+1 /wk → 2/k, so wk ∼ 2k /k! and therefore w(ρ) ∼ e2ρ .
This means we have found the diverging radial wavefunction, u(ρ) ∼ eρ , which
is in fact the correct behaviour for general values of the energy.
To find the bound states, we must choose energies such that the series is not
an infinite one. As long as the series stops somewhere, the exponential decrease
will eventually take over, and yield a finite (bound state) wavefunction. Just
as for the simple harmonic oscillator, this can only happen if for some k,
wk+1 = 0. Inspecting the ratio wk+1 /wk , evidently the condition for a bound
state is that

ν = n, integer ,

in which case the series for w(ρ) terminates at k = n − % − 1. From now on,
since we know that for the functions we’re interested in ν is an integer, we
replace ν by n.
Finally, making use of the definitions of ν and κ above, we obtain the
bound state energies,
- .2
Ze2 m 1 Z2
En = − ≡ − Ry .
4π#0 2!2 n2 n2

Remarkably, this is the very same series of bound state energies found by
Bohr from his model! Of course, this had better be the case, since the series of
energies Bohr found correctly accounted for the spectral lines emitted by hot
hydrogen atoms. Notice, though, that there are some important differences

Advanced Quantum Physics

4.4. ATOMIC HYDROGEN 41

with the Bohr model: the energy here is determined entirely by n, called the
principal quantum number, but, in contrast to Bohr’s model, n is not the
angular momentum. The true ground state of the hydrogen atom, n = 1, has
zero angular momentum: since n = k + % + 1, n = 1 means both l = 0 and
k = 0. The ground state wavefunction is therefore spherically symmetric, and
the function w(ρ) = w0 is just a constant. Hence u(ρ) = ρe−ρ w0 and the actual
radial wavefunction is this divided by r, and of course suitably normalized.
To write the wavefunction
$ in terms of r, we need to find κ. Putting together
ρ = κn r, κn = −2mEn /!2 and the expression for En , we find that κn =
Ze2 m
4π%0 !2 n = na0 , where
Z

4π#0 !2
a0 = = 0.529 × 10−10 m
me2
denotes the Bohr radius – the radius of the lowest orbit in Bohr’s model.2
1 (Ze) 1
With this definition, the energy levels can then be expressed as En = − 4π%0 2a0 n
2.
Moving on to the excited states: for n = 2, we have a choice: either
the radial function w(ρ) can have one term, as before, but now the angular
momentum % = 1 (since n = k + % + 1); or w(ρ) can have two terms (so k = 1),
and % = 0. Both options give the same energy, 0.25 Ry, since n is the same,
and the energy only depends on n. In fact, there are four states at this energy,
since % = 1 has states with m = 1, m = 0 and m = 1, and % = 0 has the one
state m = 0. For n = 3, there are 9 states altogether: % = 0 gives one, % = 1
gives 3 and % = 2 gives 5 different m values. In fact, for principal quantum
number n there are n2 degenerate states (n2 being the sum of the first n odd
integers).
From now on, we label the wavefunctions with the quantum numbers,
ψn!m (r, θ, φ), so the ground state is the spherically symmetric ψ100 (r). For
this state R(r) = u(r)/r, where u(ρ) = e−ρ ρ!+1 w(ρ) = e−ρ ρw0 , with w0 a
constant and ρ = κ1 r = Zr/a0 . So, as a function of r, R10 (r) = N e−Zr/a0
with N the normalization constant:
- .3
Z 2 −Zr/a0
R10 = 2 e .
a0
For n = 2, % = 1 the function w(ρ) is still a single term, a constant, but
now u(ρ) = e−ρ ρ!+1 w(ρ) = e−ρ ρ2 w0 , and, for n = 2, ρ = κ2 r = Zr/2a0 ,
remembering the energy-dependence of κ. After normalization, we find
- .3/2 - .
1 Z Zr
R21 = √ e−Zr/2a0 .
2 6 a0 a0
The other n = 2 state has % = 0. So from n = k + % + 1, we have k = 1 and
the series for w has two terms, k = 0 and k = 1, the ratio being
wk+1 2(k + % + 1 − n)
= = −1 ,
wk (k + 1)(k + 2(% + 1))
for the relevant values: k = 0, % = 0, n = 2. So w1 = −w0 , w(ρ) = w0 (1 − ρ).
For n = 2, ρ = r/2a0 , the normalized wavefunction is given by
- .3/2 - .
1 Z 1 Zr
R20 = √ 1− e−Zr/2a0 .
2 a0 2 a0
Note that the zero angular momentum wavefunctions are non-zero and have
non-zero slope at the origin. This means that the full three-dimensional wave-
functions have a slope discontinuity there! But this is fine - the potential is

Advanced Quantum Physics

4.4. ATOMIC HYDROGEN 42

infinite at the origin. (Actually, the proton is not a point charge, so really the
kink will be smoothed out over a volume of the size of the proton - a very tiny
effect.)
In practice, the first few radial functions w(ρ) can be constructed fairly
easily using the method presented above, but it should be noted that the
differential equation for w(ρ),

ρ∂ρ2 w(ρ) + 2(% + 1 − ρ)∂ρ w(ρ) + 2(n − (% + 1))w(ρ) = 0 ,

is in fact Laplace’s equation, usually written

(z∂z2 + (k − 1 − z)∂z + p)Lkp (z) = 0 ,

where k, p are integers, and Lkp (z) is a Laguerre polynomial. The two
equations are the same if z = 2ρ, and the solution to the radial equation is
therefore,

wn! (ρ) = L2!+1

n−!−1 (2ρ) .

The Laguerre polynomials L0p (z), and associated Laguerre polynomials

Lkp (z) are given by:

dp −z p dp 0
L0p (z) = ez (e z ), Lkp (z) = (−1)k L (z) .
dz p dz p p+k
(These representations can be found neatly by solving Laplace’s equation using
- surprise - a Laplace transform.) The polynomials satisfy the orthonormality
relations (with the mathematicians’ normalization convention)
+ ∞
[(p + k)!]3
e−z z k Lkp Lkq dz = δpq .
0 p!

But what do the polynomials look like? The function e−z z p is zero at
the origin (apart from the trivial case p = 0) and zero at infinity, always
positive and having non-zero slope except at its maximum value, z = p. The p
derivatives bring in p separated zeroes, easily checked by sketching the curves
generated by successive differentiation. Therefore, L0p (z), a polynomial of
degree p, has p real positive zeroes, and value at the origin L0p (0) = p!, since
the only non-zero term at z = 0 is that generated by all p differential operators
acting on z p .
The associated Laguerre polynomial Lkp (z) is generated by differentiating
Lp+k (z) k times. Now L0p+k (z) has p + k real positive zeroes, differentiating
0

it gives a polynomial one degree lower, with zeroes which must be one in
each interval between the zeroes of L0p+k (z). This argument remains valid for
successive derivatives, so Lkp (z) must have p real separate zeroes.
Putting all this together, and translating back from ρ to r, the radial
solutions are given by,
- .
Zr ! 2!+1
Rn! (r) = N e−Zr/na0 Ln−!−1 (2Zr/na0 ) ,
na0
with N the normalization constant. For a given principle quantum number
n,the largest % radial wavefunction is given by Rn,n−1 ∝ rn−1 e−Zr/na0 .

$ Info. The eigenvalues of the Hamiltonian for the hydrogen exhibit an unex-
pectedly high degeneracy. The fact that En!m is independent of m is common to all
central potentials – it is just a reflection of rotational invariance of the Hamiltonian.

Advanced Quantum Physics

4.4. ATOMIC HYDROGEN 43

However, the degeneracy of different % values with the same principle quantum num-
ber is considered “accidental”, a peculiarity of the 1/r potential. To understand the
origin of the degeneracy for atomic hydrogen, it is helpful to reflect first on
the classical dynamics.
In classical mechanics, central forces also lead to conservation of angular momen-
tum leaving orbits restricted to lie in a plane. However, for 1/r type potentials, these
orbits are also closed, i.e. they do not precess. In classical mechanics, this implies
that there is an additional conserved vector, since the direction of the major axis of
the elliptical orbit is a constant of the motion. This direction is determined by the
Runge-Lenz vector,
1 e2 r
R= p×L− .
m 4π#0 r
In quantum theory, up to an operator ordering prescription, R becomes an operator,
1 e2 r
R̂ = (p̂ × L̂ − L̂ × p̂) − .
2m 4π#0 r
With this definition, one may confirm that [Ĥ, R̂] = 0 (exercise).
As a vector operator, R̂ exhibits the following commutation relations, [R̂i , L̂j ] =
i!#ijk R̂k . Similarly, [R̂i , N̂j ] = i! (−2 Ĥ)
m #ijk L̂k (exercise). Moreover, one may confirm
that
- 2 .2
e 2Ĥ 2
R̂2 = + (L̂ + !2 ) ,
4π#0 m
showing that Ĥ can be written in terms of the two constants of motion, L̂2 )
and R̂2 .
Focussing on the bound states, if we consider the Hermitian operator, K̂ = −m 2Ĥ
R̂,
which fulfil the following commutation relations, [K̂i , K̂j ] = i!#ijk L̂k , [K̂i , L̂j ] =
i!#ijk K̂k , and [L̂i , L̂j ] = i!#ijk L̂k , we find that
- 2 .2
e m
Ĥ = − .
4π#0 2(K̂ + L̂2 + !2 )
2

If we now define the “raising and lowering” operators, M̂ = 2 ,

L̂+K̂
N̂ = L̂−K̂
2 the
following commutation relations emerge (exercise),
[M̂i , M̂j ] = i!#ijk L̂k
[N̂i , N̂j ] = i!#ijk K̂k
[N̂i , M̂j ] = 0 ,
i.e. we have obtained two commuting angular momentum algebras(!) and
- 2 .2
e m
Ĥ = − .
4π#0 2(2M̂ + 2N̂2 + !2 )
2

We can simultaneously diagonalize the operators, M̂2 , M̂z , N̂2 and N̂z ,
M̂2 |m, n, µ, ν$ = !2 m(m + 1)|m, n, µ, ν$, M̂z |m, n, µ, ν$ = !µ|m, n, µ, ν$
N̂ |m, n, µ, ν$ = ! m(m + 1)|m, n, µ, ν$,
2 2
N̂z |m, n, µ, ν$ = !ν|m, n, µ, ν$ .
where m, n = 0, 1/2, 1, 3/2, · · ·, µ = −m, −m + 1, · · · m and ν = −n, −n + 1, · · · n.
Since R̂ · L̂ = L̂ · R̂ = 0, then K̂ · L̂ = L̂ · R̂ = 0 and the only relevant states are those
for which M̂2 − N̂2 = 0, i.e. m = n. Therefore,
- 2 .2
e m
Ĥ|m, m, µ, ν$ = − |m, m, µ, ν$
4π#0 2!2 (4m(m + 1) + 1)
- 2 .2
e m
=− |m, m, µ, ν$ .
4π#0 2!2 (2m + 1)2
From this result, we can identify 2m + 1 = 1, 2, · · · as the principle quantum number.
For a given (2m + 1) value, the degeneracy of the state is (2m + 1)2 as expected.

Advanced Quantum Physics

Chapter 5

Motion of a charged particle

in a magnetic field
Hendrik Antoon Lorentz 1853-
Hitherto, we have focussed on applications of quantum mechanics to free parti- 1928
A Dutch physi-
cles or particles confined by scalar potentials. In the following, we will address cist who shared
the influence of a magnetic field on a charged particle. Classically, the force on the 1902 Nobel
Prize in Physics
a charged particle in an electric and magnetic field is specified by the Lorentz with Pieter Zee-
force law: man for the dis-
covery and the-
oretical explana-
F = q (E + v × B) , tion of the Zee-
man effect. He
where q denotes the charge and v the velocity. (Here we will adopt a convention also derived the transformation equa-
tions subsequently used by Albert
in which q denotes the charge (which may be positive or negative) and e ≡ |e| Einstein to describe space and time.
denotes the modulus of the electron charge, i.e. for an electron, the charge
q = −e = −1.602176487 × 10−19 C.) The velocity-dependent force associated Joseph-Louis Lagrange, born
Giuseppe Lodovico Lagrangia
with the magnetic field is quite different from the conservative forces associated 1736-1813
with scalar potentials, and the programme for transferring from classical to An Italian-born
quantum mechanics - replacing momenta with the appropriate operators - has mathematician
and astronomer,
to be carried out with more care. As preparation, it is helpful to revise how who lived most
the Lorentz force arises in the Lagrangian formulation of classical mechanics. of his life in
Prussia and
France, mak-
ing significant
5.1 Classical mechanics of a particle in a field contributions
to all fields of analysis, to number
For a system with m degrees of freedom specified by coordinates q1 , · · · qm , the theory, and to classical and celestial
mechanics. On the recommendation
classical action is determined from the Lagrangian L(qi , q̇i ) by of Euler and D’Alembert, in 1766
Lagrange succeeded Euler as the
! director of mathematics at the
S[qi ] = dt L(qi , q̇i ) . Prussian Academy of Sciences in
Berlin, where he stayed for over
twenty years, producing a large
body of work and winning several
The action is said to be a functional of the coordinates qi (t). According prizes of the French Academy of
to Hamilton’s extremal principle (also known as the principle of least Sciences. Lagrange’s treatise on
analytical mechanics, written in
action), the dynamics of a classical system is described by the equations that Berlin and first published in 1788,
minimize the action. These equations of motion can be expressed through the offered the most comprehensive
treatment of classical mechanics
classical Lagrangian in the form of the Euler-Lagrange equations, since Newton and formed a basis for
the development of mathematical
d physics in the nineteenth century.
(∂q̇ L(qi , q̇i )) − ∂qi L(qi , q̇i ) = 0 . (5.1)
dt i

" Info. Euler-Lagrange equations: According to Hamilton’s extremal princi-

ple, for any smooth set of curves wi (t), the variation of the action around the classical
solution qi (t) is zero, i.e. lim!→0 1! (S[qi + #wi ] − S[qi ]) = 0. Applied to the action,

Advanced Quantum Physics

5.1. CLASSICAL MECHANICS OF A PARTICLE IN A FIELD 45

"
the variation implies that, for any i, dt (wi ∂qi L(qi , q̇i ) + ẇi ∂q̇i L(qi , q̇i )) = 0. Then,
integrating the second term by parts, and droping the boundary term, one obtains
! # $
d
dt wi ∂qi L(qi , q̇i ) − ∂q̇i L(qi , q̇i ) = 0 .
dt
Since this equality must follow for any function wi (t), the term in parentheses in the
integrand must vanish leading to the Euler-Lagrange equation (5.1).

The canonical momentum is specified by the equation pi = ∂q̇i L, and

the classical Hamiltonian is defined by the Legendre transform,
%
H(qi , pi ) = pi qi − L(qi , q̇i ) . (5.2)
i

It is straightforward to check that the equations of motion can be written in

the form of Hamilton’s equations of motion,

q̇i = ∂pi H, ṗi = −∂qi H . Siméon Denis Poisson 1781-

1840
A French
From these equations it follows that, if the Hamiltonian is independent of a mathematician,
particular coordinate qi , the corresponding momentum pi remains constant. geometer, and
physicist whose
For conservative forces,1 the classical Lagrangian and Hamiltonian can be mathematical
written as L = T − V , H = T + V , with T the kinetic energy and V the skills enabled
potential energy. him to compute
the distribution
of electrical
" Info. Poisson brackets: Any dynamical variable f in the system is some charges on the surface of conduc-
tors. He extended the work of his
function of the phase space coordinates, the qi s and pi s, and (assuming it does not mentors, Pierre Simon Laplace and
depend explicitly on time) its time-development is given by: Joseph Louis Lagrange, in celestial
mechanics by taking their results to a
d
f (qi , pi ) = ∂qi f q̇i + ∂pi f ṗi = ∂qi f ∂pi H − ∂pi f ∂qi H ≡ {f, H}. higher order of accuracy. He was also
dt known for his work in probability.

The curly brackets are known as Poisson brackets, and are defined for any dynamical
variables as {A, B} = ∂qi A ∂pi B − ∂pi A ∂qi B. From Hamilton’s equations, we have
shown that for any variable, f˙ = {f, H}. It is easy to check that, for the coordinates
and canonical momenta, {qi , qj } = 0 = {pi , pj }, {qi , pj } = δij . This was the
classical mathematical structure that led Dirac to link up classical and quantum
mechanics: He realized that the Poisson brackets were the classical version of the
commutators, so a classical canonical momentum must correspond to the quantum
differential operator in the corresponding coordinate.2
With these foundations revised, we now return to the problem at hand; the
infleunce of an electromagnetic field on the dynamics of the charged particle.
As the Lorentz force is velocity dependent, it can not be expressed simply
as the gradient of some potential. Nevertheless, the classical path traversed by
a charged particle is still specifed by the principle of least action. The electric
and magnetic fields can be written in terms of a scalar and a vector potential
as B = ∇×A, E = −∇φ− Ȧ. The corresponding Lagrangian takes the form:3
1
L = mv2 − qφ + qv · A.
2
1
i.e. forces that conserve mechanical energy.
2
For a detailed discussion, we refer to Paul A. M. Dirac, Lectures on Quantum Mechanics,
Belfer Graduate School of Science Monographs Series Number 2, 1964.
3
In a relativistic formulation, the interaction term
R here looks less arbitrary: the relativistic
version would have the relativistically invariant q Aµ dxµ added to the action integral, where
the four-potential Aµ = (φ, A) and dxµ = (ct, dx1 , dx2 , dx3 ). This is the simplest possible
invariant interaction between theR electromagnetic field and
R the particle’s four-velocity. Then,
in the non-relativistic limit, q Aµ dxµ just becomes q (v · A − φ)dt.

Advanced Quantum Physics

5.2. QUANTUM MECHANICS OF A PARTICLE IN A FIELD 46

In this case, the general coordinates qi ≡ xi = (x1 , x2 , x3 ) are just the Carte-
sian coordinates specifying the position of the particle, and the q̇i are the three
components ẋi = (ẋ1 , ẋ2 , ẋ3 ) of the particle velocities. The important point is
that the canonical momentum

pi = ∂ẋi L = mvi + qAi ,

is no longer simply given by the mass × velocity – there is an extra term!

Making use of the definition (5.2), the corresponding Hamiltonian is given
by
% 1 1
H(qi , pi ) = (mvi + qAi ) vi − mv2 + qφ − qv · A = mv2 + qφ .
2 2
i

Reassuringly, the Hamiltonian just has the familiar form of the sum of the
kinetic and potential energy. However, to get Hamilton’s equations of motion,
the Hamiltonian has to be expressed solely in terms of the coordinates and
canonical momenta, i.e.
1
H= (p − qA(r, t))2 + qφ(r, t) .
2m
Let us now consider Hamilton’s equations of motion, ẋi = ∂pi H and
ṗi = −∂xi H. The first equation recovers the expression for the canonical
momentum while second equation yields the Lorentz force law. To under-
stand how, we must first keep in mind that dp/dt is not the acceleration: The
A-dependent term also varies in time, and in a quite complicated way, since
it is the field at a point moving with the particle. More precisely,
& '
ṗi = mẍi + q Ȧi = mẍi + q ∂t Ai + vj ∂xj Ai ,

where we have assumed a summation over repeated indicies. The right-hand

side of the second of Hamilton’s equation, ṗi = − ∂x
∂H
i
, is given by
1
−∂xi H = (p − qA(r, t))q∂xi A − q∂xi φ(r, t) = qvj ∂xi Aj − q∂xi φ .
m
& '
Together, we obtain the equation of motion, mẍi = −q ∂t Ai + vj ∂xj Ai +
qvj ∂xi Aj − q∂xi φ. Using the identity, v × (∇ × A) = ∇(v · A) − (v · ∇)A, and
the expressions for the electric and magnetic fields in terms of the potentials,
one recovers the Lorentz equations

mẍ = F = q (E + v × B) .

With these preliminary discussions of the classical system in place, we are now
in a position to turn to the quantum mechanics.

5.2 Quantum mechanics of a particle in a field

To transfer to the quantum mechanical regime, we must once again implement
the canonical quantization procedure setting p̂ = −i!∇, so that [x̂i , p̂j ] =
i!δij . However, in this case, p̂i %= mv̂i . This leads to the novel situation that
the velocities in different directions do not commute.4 To explore influence of
the magnetic field on the particle dynamics, it is helpful to assess the relative
weight of the A-dependent contributions to the quantum Hamiltonian,
1
Ĥ = (p̂ − qA(r, t))2 + qφ(r, t) .
2m
4 i!q
With mv̂i = −i!∂xi − qAi , it is easy (and instructive) to verify that [v̂x , v̂y ] = m2
B.

Advanced Quantum Physics

5.3. ATOMIC HYDROGEN: NORMAL ZEEMAN EFFECT 47

Expanding the square on the right hand side of the Hamiltonian, the
cross-term (known as the paramagnetic term) leads to the contribution
q!
− 2im (∇ · A + A · ∇) = iq!
m A · ∇, where the last equality follows from the
Coulomb gauge condition, ∇ · A = 0.5 Combined with the diamagnetic (A2 )
contribution, one obtains the Hamiltonian,
!2 2 iq! q2 2
Ĥ = −
∇ + A·∇+ A + qφ .
2m m 2m
For a constant magnetic field, the vector potential can be written as A =
−r × B/2. In this case, the paramagnetic component takes the form
iq! iq! q
A·∇= (r × ∇) · B = − L · B,
m 2m 2m
where L denotes the angular momentum operator (with the hat not shown for
brevity!). Similarly, the diamagnetic term leads to
q2 2 q2 & 2 2 ' q2B 2 2
A = r B − (r · B)2 = (x + y 2 ) ,
2m 8m 8m
where, here, we have chosen the magnetic field to lie along the z-axis.

5.3 Atomic hydrogen: Normal Zeeman effect

Before addressing the role of these separate contributions in atomic hydrogen,
let us first estimate their relative magnitude. With &x2 + y 2 ' ( a20 , where a0
denotes the Bohr radius, and &Lz ' ( !, the ratio of the paramagnetic and
diamagnetic terms is given by
(q 2 /8me )&x2 + y 2 'B 2 e a20 B 2
= ( 10−6 B/T .
(q/2me )&Lz 'B 4 !B
Therefore, while electrons remain bound to atoms, for fields that can be
achieved in the laboratory (B ( 1 T), the diamagnetic term is negligible as
compared to the paramagnetic term. Moreover, when compared with the
Coulomb energy scale,
eB!/2me e! B/T
= B( ,
me c2 α2 /2 (me cα)2 2.3 × 105
2
where α = 4π# e 1
0 !c
1
( 137 denotes the fine structure constant, one may see
that the paramagnetic term provides only a small perturbation to the typical
atomic splittings.
5 Splitting of the sodium D lines
The electric field E and magnetic field B of Maxwell’s equations contain only “physical”
due to an external magnetic field.
degrees of freedom, in the sense that every mathematical degree of freedom in an electromag-
netic field configuration has a separately measurable effect on the motions of test charges in
The multiplicity of the lines and
the vicinity. As we have seen, these “field strength” variables can be expressed in terms of their “selection rule” will be dis-
the scalar potential φ and the vector potential A through the relations: E = −∇φ − ∂t A cussed more fully in chapter 9.
and B = ∇ × A. Notice that if A is transformed to A + ∇Λ, B remains unchanged, since The figure is taken from the orig-
B = ∇ × [A + ∇Λ] = ∇ × A. However, this transformation changes E as inal paper, P. Zeeman, The effect
of magnetization on the nature of
E = −∇φ − ∂t A − ∇∂t Λ = −∇[φ + ∂t Λ] − ∂t A .
light emitted by a substance, Na-
If φ is further changed to φ − ∂t Λ, E remains unchanged. Hence, both the E and B fields ture 55, 347 (1897).
are unchanged if we take any function Λ(r, t) and simultaneously transform
A → A + ∇Λ
φ → φ − ∂t Λ .
A particular choice of the scalar and vector potentials is a gauge, and a scalar function Λ
used to change the gauge is called a gauge function. The existence of arbitrary numbers of
gauge functions Λ(r, t), corresponds to the U(1) gauge freedom of the theory. Gauge fixing
can be done in many ways.

Advanced Quantum Physics

5.4. GAUGE INVARIANCE AND THE AHARONOV-BOHM EFFECT 48

However, there are instances when the diamagnetic contriubution can play
an important role. Leaving aside the situation that may prevail on neutron
stars, where magnetic fields as high as 108 T may exist, the diamagnetic con-
tribution can be large when the typical “orbital” scale &x2 + y 2 ' becomes
macroscopic in extent. Such a situation arises when the electrons become
unbound such as, for example, in a metal or a synchrotron. For a further
discussion, see section 5.5 below.
Retaining only the paramagnetic contribution, the Hamiltonian for a “spin-
less” electron moving in a Coulomb potential in the presence of a constant
magnetic field then takes the form,
e
Ĥ = Ĥ0 + BLz ,
2m
2
p̂ 2
where Ĥ0 = 2m e
− 4π# 0r
. Since [Ĥ0 , Lz ] = 0, the eigenstates of the unperturbed
Hamiltonian, ψl$m (r) remain eigenstates of Ĥ and the corresponding energy
levels are specified by
Ry
En$m = − + !ωL m
n2
Sir Joseph Larmor 1857-1942
where ωL = 2m eB
denotes the Larmor frequency. From this result, we expect A physicist and
that a constant magnetic field will lead to a splitting of the (2)+1)-fold degen- mathematician
who made in-
eracy of the energy levels leading to multiplets separated by a constant energy novations in the
shift of !ωL . The fact that this behaviour is not recapitulated generically by understanding
of electricity,
experiment was one of the key insights that led to the identification of electron dynamics, ther-
spin, a matter to which we will turn in chapter 6. modynamics,
and the electron theory of matter.
His most influential work was Aether
and Matter, a theoretical physics
5.4 Gauge invariance and the Aharonov-Bohm ef- book published in 1900. In 1903 he
fect was appointed Lucasian Professor of
Mathematics at Cambridge, a post
he retained until his retirement in
Our derivation above shows that the quantum mechanical Hamiltonian of a 1932.
charged particle is defined in terms of the vector potential, A. Since the latter
is defined only up to some gauge choice, this suggests that the wavefunction
is not a gauge invariant object. Indeed, it is only the observables associated
with the wavefunction which must be gauge invariant. To explore this gauge
freedom, let us consider the influence of the gauge transformation,

A )→ A" = A + ∇Λ, φ )→ φ" − ∂t Λ ,

where Λ(r, t) denotes a scalar function. Under the gauge transformation, one
may show that the corresponding wavefunction gets transformed as
( q )
ψ " (r, t) = exp i Λ(r, t) ψ(r, t) . (5.3)
!

" Exercise. If wavefunction ψ(r, t) obeys the time-dependent Schrödinger equa-

tion, i!∂t ψ = Ĥ[A, φ]ψ, show that ψ " (r, t) as defined by (5.3) obeys the equation
i!∂t ψ " = Ĥ " [A" , φ" ]ψ " .

The gauge transformation introduces an additional space and time-dependent

phase factor into the wavefunction. However, since the observable translates
to the probability density, |ψ|2 , this phase dependence seems invisible.

" Info. One physical manifestation of the gauge invariance of the wavefunction
is found in the Aharonov-Bohm effect. Consider a particle with charge q travelling

Advanced Quantum Physics

5.4. GAUGE INVARIANCE AND THE AHARONOV-BOHM EFFECT 49

Figure 5.1: (Left) Schematic showing the geometry of an experiment to observe the
Aharonov-Bohm effect. Electrons from a coherent source can follow two paths which
encircle a region where the magnetic field is non-zero. (Right) Interference fringes
for electron beams passing near a toroidal magnet from the experiment by Tonomura
and collaborators in 1986. The electron beam passing through the center of the torus
acquires an additional phase, resulting in fringes that are shifted with respect to
those outside the torus, demonstrating the Aharonov-Bohm effect. For details see the
original paper from which this image was borrowed see Tonomura et al., Evidence
for Aharonov-Bohm effect with magnetic field completely shielded from electron wave,
Phys. Rev. Lett. 56, 792 (1986).

along a path, P , in which the magnetic field, B = 0 is identically zero. However, a

vanishing of the magnetic field does not imply that the vector potential, A is zero.
Indeed, as we have seen, any Λ(r) such that A = ∇Λ will translate to this condition.
In traversing
" the path, the wavefunction of the particle will acquire the phase factor
ϕ = !q P A · dr, where the line integral runs along the path.
If we consider now two separate paths P and P " which share the same initial and
final points, the relative phase of the wavefunction will be set by
! ! * !
q q q q
∆ϕ = A · dr − A · dr = A · dr = B · d2 r ,
! P ! P! ! ! A Sir George Gabriel Stokes, 1st
+ " Baronet 1819-1903
where the line integral runs over the loop involving paths P and P " , and A runs A mathematician
over the area enclosed by the loop. The last relation follows from the application of and physicist,
who at Cam-
Stokes’ theorem. This result shows that the" relative phase ∆ϕ is fixed by the factor
bridge made
q/! multiplied by the magnetic flux Φ = A B · d2 r enclosed by the loop.6 In the important con-
absence of a magnetic field, the flux vanishes, and there is no additional phase. tributions to
However, if we allow the paths to enclose a region of non-vanishing magnetic fluid dynamics
(including the
field (see figure 5.1(left)), even if the field is identically zero on the paths P and P " , NavierStokes
the wavefunction will acquire a non-vanishing relative phase. This flux-dependent equations), optics, and mathematical
phase difference translates to an observable shift of interference fringes when on an physics (including Stokes’ theorem).
observation plane. Since the original proposal,7 the Aharonov-Bohm effect has been He was secretary, and then president,
of the Royal Society.
studied in several experimental contexts. Of these, the most rigorous study was un-
dertaken by Tonomura in 1986. Tomomura fabricated a doughnut-shaped (toroidal)
ferromagnet six micrometers in diameter (see figure 5.1b), and covered it with a nio-
bium superconductor to completely confine the magnetic field within the doughnut, in
accordance with the Meissner effect.8 With the magnet maintained at 5 K, they mea-
sured the phase difference from the interference fringes between one electron beam
passing though the hole in the doughnut and the other passing on the outside of
the doughnut. The results are shown in figure 5.1(right,a). Interference fringes are
displaced with just half a fringe of spacing inside and outside of the doughnut, indi-
cating the existence of the Aharonov-Bohm effect. Although electrons pass through
regions free of any electromagnetic field, an observable effect was produced due to the
existence of vector potentials.
6
Note that the phase difference depends on the magnetic flux, a function of the magnetic
field, and is therefore a gauge invariant quantity.
7
Y. Aharonov and D. Bohm, Significance of electromagnetic potentials in quantum theory,
Phys. Rev. 115, 485 (1959).
8
Perfect diamagnetism, a hallmark of superconductivity, leads to the complete expulsion
of magnetic fields – a phenomenon known as the Meissner effect.

Advanced Quantum Physics

5.5. FREE ELECTRONS IN A MAGNETIC FIELD: LANDAU LEVELS 50

The observation of the half-fringe spacing reflects the constraints imposed by

the superconducting toroidal shield. When a superconductor completely surrounds
a magnetic flux, the flux is quantized to an integral multiple of quantized flux h/2e,
the factor of two reflecting that fact that the superconductor involves a condensate of
electron pairs. When an odd number of vortices are enclosed inside the superconduc-
tor, the relative phase shift becomes π (mod. 2π) – half-spacing! For an even number
of vortices, the phase shift is zero.9

Lev Davidovich Landau 1908-

5.5 Free electrons in a magnetic field: Landau levels 1968
A prominent
Soviet physicist
Finally, to complete our survey of the influence of a uniform magnetic field on who made
the dynamics of charged particles, let us consider the problem of a free quan- fundamental
contributions
tum particle. In this case, the classical electron orbits can be macroscopic and to many areas
there is no reason to neglect the diamagnetic contribution to the Hamiltonian. of theoretical
physics. His
Previously, we have worked with a gauge in which A = (−y, x, 0)B/2, giving a accomplishments
constant field B in the z-direction. However, to address the Schrödinger equa- include the
tion for a particle in a uniform perpendicular magnetic field, it is convenient co-discovery of the density matrix
method in quantum mechanics,
to adopt the Landau gauge, A(r) = (−By, 0, 0). the quantum mechanical theory of
diamagnetism, the theory of super-
fluidity, the theory of second order
" Exercise. Construct the gauge transformation, Λ(r) which connects these phase transitions, the Ginzburg-
two representations of the vector potential. Landau theory of superconductivity,
the explanation of Landau damping
in plasma physics, the Landau pole
In this case, the stationary form of the Schrödinger equation is given by in quantum electrodynamics, and the
two-component theory of neutrinos.
1 , - He received the 1962 Nobel Prize
Ĥψ(r) = (p̂x + qBy)2 + p̂2y + p̂2z ψ(r) = Eψ(r) . in Physics for his development of a
2m mathematical theory of superfluidity
that accounts for the properties of
Since Ĥ commutes with both p̂x and p̂z , both operators have a common set of liquid helium II at a temperature
below 2.17K.
eigenstates reflecting the fact that px and pz are conserved by the dynamics.
The wavefunction must therefore take the form, ψ(r) = ei(px x+ipz z)/!χ(y),
with χ(y) defined by the equation,
. 2 / # $
pˆy 1 p2
+ mω 2 (y − y0 )2 χ(y) = E − z χ(y) .
2m 2 2m

Here y0 = −px /qB and ω = |q|B/m coincides with the cyclotron frequency
of the classical charged particle (exercise). We now see that the conserved
canonical momentum px in the x-direction is in fact the coordinate of the centre
of a simple harmonic oscillator potential in the y-direction with frequency ω.
As a result, we can immediately infer that the eigenvalues of the Hamiltonian
are comprised of a free particle component associated with motion parallel to
the field, and a set of harmonic oscillator states,

p2z
En,pz = (n + 1/2)!ω + .
2m
The quantum numbers, n, specify states known as Landau levels.
Let us confine our attention to states corresponding to the lowest oscillator
(Landau level) state, (and, for simplicity, pz = 0), E0 = !ω/2. What is
the degeneracy of this Landau level? Consider a rectangular geometry of
area A = Lx × Ly and, for simplicity, take the boundary conditions to be
periodic. The centre of the oscillator wavefunction, y0 = −px /qB, must lie
9
The superconducting flux quantum was actually predicted prior to Aharonov and Bohm,
by Fritz London in 1948 using a phenomenological theory.

Advanced Quantum Physics

5.5. FREE ELECTRONS IN A MAGNETIC FIELD: LANDAU LEVELS 51

between 0 and Ly . With periodic boundary conditions eipx Lx /! = 1, so that

px = n2π!/Lx . This means that y0 takes a series of evenly-spaced discrete
values, separated by ∆y0 = h/qBLx . So, for electron degrees of freedom, Klaus von Klitzing, 1943-
q = −e, the total number of states N = Ly /|∆y0 |, i.e. German physicist
who was awarded
Lx Ly B the Nobel Prize
νmax = =A , (5.4)
h/eB Φ0 for Physics in
1985 for his
where Φ0 = e/h denotes the “flux quantum”. So the total number of states in discovery that
under appropri-
the lowest energy level coincides with the total number of flux quanta making ate conditions
up the field B penetrating the area A. the resistance
offered by an
The Landau level degeneracy, νmax , depends on field; the larger the field, electrical conductor is quantized.
the more electrons can be fit into each Landau level. In the physical system, The work was first reported in the
each Landau level is spin split by the Zeeman coupling, with (5.4) applying to following reference, K. v. Klitzing, G.
Dorda, and M. Pepper, New method
one spin only. Finally, although we treated x and y in an asymmetric manner, for high-accuracy determination of
this was merely for convenience of calculation; no physical quantity should the fine-structure constant based
on quantized Hall resistance, Phys.
dierentiate between the two due to the symmetry of the original problem. Rev. Lett. 45, 494 (1980).

" Exercise. Consider the solution of the Schrödinger equation when working in
the symmetric gauge with A = −r × B/2. Hint: consider the velocity commutation
relations, [vx , vy ] and how these might be deployed as conjugate variables.

" Info. It is instructive to infer y0 from purely classical considerations: Writing

mv̇ = qv × B in component form, we have mẍ = qB qB
c ẏ, mÿ = − c ẋ, and mz̈ = 0.
Focussing on the motion in the xy-plane, these equations integrate straightforwardly
to give, mẋ = qB qB
c (y − y0 ), mẏ = − c (x − x0 ). Here (x0 , y0 ) are the coordinates of
the centre of the classical circular motion (known as the “guiding centre”) – the
velocity vector v = (ẋ, ẏ) always lies perpendicular to (r − r0 ), and r0 is given by
y0 = y − mvx /qB = −px /qB, x0 = x + mvy /qB = x + py /qB .
(Recall that we are using the gauge A(x, y, z) = (−By, 0, 0), and px = ∂ẋ L =
mvx + qAx , etc.) Just as y0 is a conserved quantity, so is x0 : it commutes with the
Hamiltonian since [x + cp̂y /qB, p̂x + qBy] = 0. However, x0 and y0 do not commute
with each other: [x0 , y0 ] = −i!/qB. This is why, when we chose a gauge in which
y0 was sharply defined, x0 was spread over the sample. If we attempt to localize the
point (x0 , y0 ) as much as possible, it is smeared out over an area corresponding to
one flux quantum. The0natural length scale of the problem is therefore the magnetic
!
length defined by ) = qB .

" Info. Integer quantum Hall effect: Until now, we have considered the
impact of just a magnetic field. Consider now the Hall effect geometry in which
we apply a crossed electric, E and magnetic field, B. Taking into account both
contributions, the total current flow is given by
# $
j×B
j = σ0 E − ,
ne
where σ0 denotes the conductivity, and n is the electron density. With the electric
field oriented along y, and the magnetic field along z, the latter equation may be
rewritten as
# $# $ # $
1 σ0 B
jx 0
ne = σ0 .
σ0 B
− ne 1 jy Ey
Inverting these equations, one finds that
−σ02 B/ne σ0
jx = Ey , jy = Ey .
1 + (σ0 B/ne)2 1 + (σ0 B/ne)2
1 23 4 1 23 4
σxy σyy

Advanced Quantum Physics

5.5. FREE ELECTRONS IN A MAGNETIC FIELD: LANDAU LEVELS 52

Figure 5.2: (Left) A voltage V drives a current I in the positive x direction. Normal
Ohmic resistance is V /I. A magnetic field in the positive z direction shifts positive
charge carriers in the negative y direction. This generates a Hall potential and a
Hall resistance (V H/I) in the y direction. (Right) The Hall resistance varies stepwise
with changes in magnetic field B. Step height is given by the physical constant
h/e2 (value approximately 25 kΩ) divided by an integer i. The figure shows steps for
i = 2, 3, 4, 5, 6, 8 and 10. The effect has given rise to a new international standard
for resistance. Since 1990 this has been represented by the unit 1 klitzing, defined as
the Hall resistance at the fourth step (h/4e2 ). The lower peaked curve represents the
Ohmic resistance, which disappears at each step.

These provide the classical expressions for the longitudinal and Hall conductivities,
σyy and σxy in the crossed field. Note that, for these classical expressions, σxy is
proportional to B.
How does quantum mechanics revised this picture? For the classical model –
Drude theory, the random elastic scattering of electrons impurities leads to a con-
2

me , where τ
stant drift velocity in the presence of a constant electric field, σ0 = ne τ

denotes the mean time between collisions. Now let us suppose the magnetic field is
chosen so that number of electrons exactly fills all the Landau levels up to some N ,
i.e.
eB
nLx Ly = N νmax ⇒ n = N .
h
The scattering of electrons must lead to a transfer between quantum states. However,
if all states of the same energy are filled,10 elastic (energy conserving) scattering
becomes impossible. Moreover, since the next accessible Landau level energy is a
distance !ω away, at low enough temperatures, inelastic scattering becomes frozen
out. As a result, the scattering time vanishes at special values of the field, i.e. σyy → 0
and
ne e2
σxy → =N .
B h
At critical values of the field, the Hall conductivity is quantized in units of e2 /h.
Inverting the conductivity tensor, one obtains the resistivity tensor,
# $ # $−1
ρxx ρxy σxx σxy
= ,
−ρxy ρxx −σxy σxx
where
σxx σxy
ρxx = 2 + σ2
, ρxx = − 2 + σ2
,
σxx xy σxx xy

So, when σxx = 0 and σxy = νe2 /h, ρxx = 0 and ρxy = h/νe2 . The quantum
Hall state describes dissipationless current flow in which the Hall conductance σxy is
quantized in units of e2 /h. Experimental measurements of these values provides the
best determination of fundamental ratio e2 /h, better than 1 part in 107 .

10
Note that electons are subject to Pauli’s exclusion principle restricting the occupancy of
each state to unity.

Advanced Quantum Physics

Chapter 6

Spin

Until we have focussed on the quantum mechanics of particles which are “fea-
tureless”, carrying no internal degrees of freedom. However, a relativistic
formulation of quantum mechanics shows that particles can exhibit an intrin-
sic angular momentum component known as spin. However, the discovery
of the spin degree of freedom marginally predates the development of rela-
tivistic quantum mechanics by Dirac and was acheived in a ground-breaking
experiement by Stern and Gerlach (1922). In their experiment, they passed a
well-collimated beam of silver atoms through a region of inhomogeneous field
before allowing the particles to impact on a photographic plate (see figure).
The magnetic field was directed perpendicular to the beam, and has a strong
gradient, ∂z Bz != 0 so that a beam comprised of atoms with a magnetic mo-
ment would be bent towards the z or -z axis. As the magnetic moment will
be proportional to the total angular momentum, such an experiment can be
thought of as a measurement of its projection along z.
At the time of the experiment, there was an expectation that the magnetic
moment of the atom was generated in its entirety by the orbital angular mo-
mentum. As such, one would expect that there would be a minimum of three
possible values of the z-component of angular momentum: the lowest non-zero
orbital angular momentum is " = 1, with allowed values of the z-component
m!, m = 1, 0, −1. Curiously, Stern and Gerlach’s experiment (right) showed Gerlach’s postcard, dated 8th
that the beam of silver atoms split into two! This discovery, which caused February 1922, to Niels Bohr. It
great discussion and surprise presented a puzzle. shows a photograph of the beam
splitting, with the message, in
However, in our derivation of allowed angular momentum eigenvalues we
translation: “Attached [is] the
found that, although for any system the allowed values of m form a ladder experimental proof of directional
with spacing !, we could not rule out half-integral values of m. The lowest quantization. We congratulate
such case, " = 1/2, would in fact have just two allowed m values: m = ±1/2. [you] on the confirmation of your
However, such an " value could not translate to an orbital angular momentum theory.” (Physics Today Decem-
because the z-component of the orbital wavefunction, ψ has a factor e±iφ , ber 2003)
and therefore acquires a factor −1 on rotating through 2π! This would imply
that ψ is not single-valued, which doesn’t make sense for a Schrödinger-type
wavefunction.
Yet the experimental result was irrefutable. Therefore, this must be a
new kind of non-orbital angular momentum – spin. Conceptually, just as
the Earth has orbital angular momentum in its yearly circle around the sun,
and also spin angular momentum from its daily turning, the electron has an
analogous spin. But this analogy has obvious limitations: the Earth’s spin
is after all made up of material orbiting around the axis through the poles.
The electron spin cannot be imagined as arising from a rotating body, since
orbital angular momenta always come in integral multiples of !. Fortunately,
this lack of a simple quasi-mechanical picture underlying electron spin doesn’t

Advanced Quantum Physics

6.1. SPINORS, SPIN PPERATORS, PAULI MATRICES 54

prevent us from using the general angular momentum machinery developed

ealier, which followed just from analyzing the effect of spatial rotation on a
quantum mechanical system.

6.1 Spinors, spin pperators, Pauli matrices

The Hilbert space of angular momentum states for spin 1/2 is two-dimensional.
Various notations are used: |", m# becomes |s, m# or, more graphically,

|1/2, 1/2# = | ↑#, |1/2, −1/2# = | ↓# .

A general state of spin can be written as the lienar combination,

! "
α
α| ↑# + β| ↓# = ,
β

with the normalisation condition, |α|2 + |β|2 = 1, and this two-dimensional

ket is called a spinor. Operators acting on spinors are necessarily of the form
of 2 × 2 matrices. We shall adopt the usual practice of denoting the angular
momentum components Li by Si for spins. (Once again, for clarity, we also
drop the hats on the angular momentum operators!)
From our definition of the spinor, it is evident that the z-component of the Wolfgang Pauli and Niels Bohr
spin can be represented as the matrix, demonstrating ‘tippe top’ toy at
the inauguration of the new In-
! "
! 1 0 stitute of Physics at Lund, Swe-
Sz = σ z , σz = . den 1954.
2 0 −1

From the general formulae (4.5) for raising and lowering operators S± =
Sx ± iSy , with s = 1/2, we have S+ |1/2, −1/2# = !|1/2, 1/2#, S− |1/2, 1/2# =
!|1/2, −1/2#, or, in matrix form,
! " ! "
0 1 0 0
Sx + iSy = S+ = ! , Sx − iSy = S− = ! .
0 0 1 0

It therefore follows that an appropriate matrix representation for spin 1/2 is

ggiven by the Pauli spin matrices, S = !2 σ where
! " ! " ! "
0 1 0 −i 1 0
σx = , σy = , σz = . (6.1)
1 0 i 0 0 −1

These matrices are Hermitian, traceless, and obey the relations σi2 = I, σi σj =
−σj σi , and σi σj = iσk for (i, j, k) a cyclic permutation of (1, 2, 3). These
relations can be summarised by the identity,

σi σj = Iδij + i)ijk σk .

!2 2
The total spin S2 = 4 σ = 34 !2 , i.e. s(s + 1)!2 for s = 1/2.

* Exercise. Explain why any 2 × 2 matrix can be written in the form α0 I +

#
i i σi . Use your results to show that (a) (n̂ · σ) = I for any unit vector n̂, and (b)
2
α
(σ · A)(σ · B) = (A · B)I + σ · (A × B).

Advanced Quantum Physics

6.2. RELATING THE SPINOR TO THE SPIN DIRECTION 55

6.2 Relating the spinor to the spin direction

For a general state α| ↑# + β| ↓#, how do α, β relate to which way the spin
is pointing? To find out, let us assume that it is pointing up along the unit
vector n̂ = (sin θ cos φ, sin θ sin φ, cos θ), i.e. in the direction (θ, φ). In other
words, the spin is an eigenstate of the operator n̂ · σ having eigenvalue unity:
! "! " ! "
nz nx − iny α α
= .
nx + iny −nz β β

From this expression, we find that α/β = (nx − iny )/(1 − nz ) = e−iφ cot(θ/2)
(exercise). Then, making use of the normalisation, |α|2 + |β|2 = 1, we obtain
(up to an arbitrary phase)
! " ! "
α e−iφ/2 cos(θ/2)
= .
β eiφ/2 sin(θ/2)

Since e−iφ cot(θ/2) can be used to specify any complex number with 0 ≤ θ ≤ π,
0 ≤ φ < 2π, so for any possible spinor, there is an associated direction along
which the spin points up.

* Info. The spin rotation operator: In general, the rotation operator for
rotation through an angle θ about an axis in the direction of the unit vector n̂ is given
by eiθn̂·J/! where J denotes the angular momentum operator. For spin, J = S = 21 !σ,
and the rotation operator takes the form1 eiθn̂·J/! = ei(θ/2)(n̂·σ ) . Expanding the
exponential, and making use of the Pauli matrix identities ((n · σ)2 = I), one can
show that (exercise)

ei(θ/2)(n·σ ) = I cos(θ/2) + in · σ sin(θ/2) .

The rotation operator is a 2 × 2 matrix operating on the ket space. The 2 × 2

rotation matrices are unitary and form a group known as SU(2); the 2 refers to the
dimensionality, the U to their being unitary, and the S signifying determinant +1.
Note that for rotation about the z-axis, n̂ = (0, 0, 1), it is more natural to replace θ
with φ, and the rotation operator takes the form,
! −iφ/2 "
e 0
ei(θ/2)(n·σ ) = .
0 eiφ/2

In particular, the wavefunction is multiplied by −1 for a rotation of 2π. Since this is

true for any initial wave function, it is clearly also true for rotation through 2π about
any axis.

* Exercise. Construct the infinitesimal version of the rotation operator eiδθn̂·J/!

for spin 1/2, and prove that eiδθn̂·J/! σe−iδθn̂·J/! = σ + δθn̂ × σ, i.e. σ is rotated in
the same way as an ordinary three-vector - note particularly that the change depends
on the angle rotated through (as opposed to the half-angle) so, reassuringly, there
is no −1 for a complete rotation (as there cannot be - the direction of the spin is a
physical observable, and cannot be changed on rotating the measuring frame through
2π).

1
Warning: do not confuse θ – the rotation angle - with the spherical polar angle used to
parameterise n̂.

Advanced Quantum Physics

6.3. SPIN PRECESSION IN A MAGNETIC FIELD 56

6.3 Spin precession in a magnetic field

Consider a magnetized classical object spinning about it’s centre of mass, with
angular momentum L and parallel magnetic moment µ, µ = γL. The constant
γ is called the gyromagnetic ratio. Now suppose that we impose a magnetic
field B along, say, the z-direction. This will exert a torque T = µ × B =
γL × B = dL dt . This equation is easily solved and shows that the angular
momentum vector L precesses about the magnetic field direction with angular
velocity of precession ω 0 = −γB.2
In the following, we will show that precisely the same result appears in
the study of the quantum mechanics of an electron spin in a magnetic field.
The electron has magnetic dipole moment µ = γS, where γ = g 2m −e
e
and the
gyromagnetic ratio, g, is very close to 2. The Hamiltonian for the interaction
3

of the electron’s dipole moment with the magnetic field is given by Ĥ =

−µ · B = −γS · B. Hence the time development is specified by the equation
|ψ(t)# = Û (t)|ψ(0)#, with the time-evolution operator (or propagator), Û (t) =
e−iĤt/! = eiγσ·Bt/2 . However, this is nothing but the rotation operator (as
shown earlier) through an angle −γBt about the direction of B!
For an arbitrary initial spin orientation
! " ! −iφ/2 "
α e cos(θ/2)
= ,
β eiφ/2 sin(θ/2)

the propagator for a magnetic field in the z-direction is given by

! −iω t/2 "
e 0 0
U (t) = eiγσ·Bt/2 = ,
0 eiω0 t/2

so the time-dependent spinor is set by

! " ! −i(φ+ω t)/2 "
α(t) e 0 cos(θ/2)
= .
β(t) ei(φ+ω0 t)/2 sin(θ/2)

The angle θ between the spin and the field stays constant while the azimuthal
angle around the field increases as φ = φ0 +ω0 t, exactly as in the classical case.
|e|B
The frequency ω0 = gωc , where ωc = 2m e
denotes the cyclotron frequency. For
a magnetic field of 1 T, ωc ( 10 rads/s.
11

* Exercise. For a spin initially pointing along the x-axis, prove that )Sx (t)# =
(!/2) cos(ω0 t).

6.3.1 Paramagnetic Resonance

The analysis above shows that the spin precession frequency is independent
of the angle of the spin with respect to the field direction. Consider then
how this looks in a frame of reference which is itself rotating with angular
velocity ω about the z-axis. Let us specify the magnetic field B0 = B0 ẑ, since
we’ll soon be adding another component. In the rotating frame, the observed
precession frequency is ω r = −γ(B0 + ω/γ), so there is a different effective
dL
2
Proof: From the equation of motion, with L+ = Lx + iLy , dt+ = −iγBL+ , L+ =
L0+ e−iγBt . Of course, dL
dt
z
= 0, since dL
dt
= γL × B is perpendicular to B, which is in the
z-direction.
3
This g-factor terminology is used more widely: the magnetic moment of an atom is
e!
written µ = gµB , where µB = 2m e
is the known as the Bohr magneton, and g depends
on the total orbital angular momentum and total spin of the particular atom.

Advanced Quantum Physics

6.3. SPIN PRECESSION IN A MAGNETIC FIELD 57

field (B0 + ω/γ) in the rotating frame. Obviously, if the frame rotates exactly
at the precession frequency, ω = ω 0 = −γB0 , spins pointing in any direction
will remain at rest in that frame – there is no effective field at all.
Suppose we now add a small rotating magnetic field with angular frequency
ω in the xy plane, so the total magnetic field,

B = B0 ẑ + B1 (êx cos(ωt) − êy sin(ωt)) .

The effective magnetic field in the frame rotating with the same frequency ω
as the small added field is then given by

Br = (B0 + ω/γ)ẑ + B1 êx .

Now, if we tune the angular frequency of the small rotating field so that it
exactly matches the precession frequency in the original static magnetic field,
ω = ω 0 = −γB0 , all the magnetic moment will see in the rotating frame is the
small field in the x-direction! It will therefore precess about the x-direction
at the slow angular speed γB1 . This matching of the small field rotation
frequency with the large field spin precession frequency is the “resonance”.
If the spins are lined up preferentially in the z-direction by the static field,
and the small resonant oscillating field is switched on for a time such that
γB1 t = π/2, the spins will be preferentially in the y-direction in the rotating
frame, so in the lab they will be rotating in the xy plane, and a coil will pick
up an a.c. signal from the induced e.m.f.

* Info. Nuclear magnetic resonance is an important tool in chemical anal-

ysis. As the name implies, the method uses the spin magnetic moments of nuclei
(particularly hydrogen) and resonant excitation. Magnetic resonance imaging
uses the same basic principle to get an image (of the inside of a body for example). In
basic NMR, a strong static B field is applied. A spin 1/2 proton in a hydrogen nucleus
then has two energy eigenstates. After some time, most of the protons fall into the
lower of the two states. We now use an electromagnetic wave (RF pulse) to excite
some of the protons back into the higher energy state. The proton’s magnetic moment
interacts with the oscillating B field of the EM wave through the Hamiltionian,
gp e gp e! gp
Ĥ = −µ · B = S·B= σ · B = µN σ · B ,
2mp c 4mp c 2

where the gyromagnetic ratio of the proton is about +5.6. The magnetic moment is
2.79µN (nuclear magnetons). Different nuclei will have different gyromagnetic ratios
giving more degrees of freedom with which to work. The strong static B field is chosen
to lie in the z direction and the polarization of the oscillating EM wave is chosen so
that the B field points in the x direction. The EM wave has (angular) frequency ω,
! "
gp gp Bz Bx cos(ωt)
Ĥ = µN Bz σz + Bx cos(ωt)σx = µN .
2 2 Bx cos(ωt) −Bz

If we now apply the time-dependent Schrödinger equation, i!∂t χ = Ĥχ, i.e.

! " ! "! "
ȧ ω0 ωI cos(ωt) a
= −i ,
ḃ ωI cos(ωt) −ω0 b

where ω0 = gp µN Bz /2! and ωI = gp µN Bx /2!, we obtain,

A proton NMR spectrum of a
ωI $ i(ω−2ω0 )t %
∂t (be−iω0 t ) = − e + e−i(ω+2ω0 )t . solution containing a simple or-
2 ganic compound, ethyl benzene.
The second term oscillates rapidly and can be neglected. The first term will only Each group of signals corre-
result in significant transitions if ω ≈ 2ω0 . Note that this is exactly the condition sponds to protons in a different
that ensures that the energy of the photons in the EM field E = !ω is equal to the part of the molecule.
energy difference between the two spin states ∆E = 2!ω0 . The conservation of energy

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6.4. ADDITION OF ANGULAR MOMENTA 58

condition must be satisfied well enough to get a significant transition rate. In NMR,
we observe the transitions back to the lower energy state. These emit EM radiation
at the same frequency and we can detect it after the stronger input pulse ends (or by
more complex methods).
NMR is a powerful tool in chemical analysis because the molecular field adds
to the external B field so that the resonant frequency depends on the molecule as
well as the nucleus. We can learn about molecular fields or just use NMR to see
what molecules are present in a sample. In MRI, we typically concentrate on the one
nucleus like hydrogen. We can put a gradient in Bz so that only a thin slice of the
material has ω tuned to the resonant frequency. Therefore we can excite transitions High resolution MRI scan of a
to the higher energy state in only a slice of the sample. If we vary (in the orthogonal brain!
direction!) the B field during the decay, we can recover 3d images.

6.4 Addition of angular momenta

In subsequent chapters, it will be necessary to add angular momentum, be it
the addition of orbital and spin angular momenta, Ĵ = L̂+S, as with the study
of spin-orbit coupling in atoms, or the addition of general angular momenta,
Ĵ = Ĵ1 + Ĵ2 as occurs in the consideration of multi-electron atoms. In the
following section, we will explore three problems: The addition of two spin
1/2 degrees of freedom; the addition of a general orbital angular momentum
and spin; and the addition of spin J = 1 angular momenta. However, before
addressing these examples in turn, let us first make some general remarks.
Without specifying any particular application, let us consider the total
angular momentum Ĵ = Ĵ1 + Ĵ2 where Ĵ1 and Ĵ2 correspond to distinct
degrees of freedom, [Ĵ1 , Ĵ2 ] = 0, and the individual operators obey angular
momentum commutation relations. As a result, the total angular momentum
also obeys angular momentum commutation relations,

[Jˆi , Jˆj ] = i!)ijk Jˆk .

For each angular momentum component, the states |j1 , m1 # and |j2 , m2 # where
mi = −ji , · · · ji , provide a basis of states of the total angular momentum
operator, Ĵ2i and the projection Jˆiz . Together, they form a complete basis
which can be used to span the states of the coupled spins,4

|j1 , m1 , j2 , m2 # ≡ |j1 , m1 # ⊗ |j2 , m2 # .

These product states are also eigenstates of Jˆz with eigenvalue !(m1 + m2 ),
but not of Ĵ2 .

* Exercise. Show that [Ĵ2 , Jˆiz ] != 0.

However, for practical application, we require a basis in which the total angular
momentum operator Ĵ2 is also diagonal. That is, we must find eigenstates
|j, mj , j1 , j2 # of the four mutually commuting operators Ĵ2 , Jˆz , Ĵ21 , and Ĵ22 .
In general, the relation between the two basis can be expressed as
&
|j, mj , j1 , j2 # = |j1 , m1 , j2 , m2 #)j1 , m1 , j2 , m2 |j, mj , j1 , j2 # ,
m1 ,m2

4
Here ⊗ denotes the “direct product” and shows that the two constituent spin states
access their own independent Hilbert space.

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6.4. ADDITION OF ANGULAR MOMENTA 59

where the matrix elements are known as Clebsch-Gordon coefficients. In

general, the determination of these coefficients from first principles is a some-
what soul destroying exercise and one that we do not intend to pursue in great
detail.5 In any case, for practical purposes, such coefficients have been tabu-
lated in the literature and can be readily obtained. However, in some simple
cases, these matrix elements can be determined straightforwardly. Moreover,
the algorithmic programme by which they are deduced offer some new con-
ceptual insights.
Operationally, the mechanism for finding the basis states of the total an-
gular momentum operator follow the strategy:

1. As a unique entry, the basis state with maximal Jmax and mj = Jmax is
easy to deduce from the original basis states since it involves the product
of states of highest weight,

|Jmax , mj = Jmax , j1 , j2 # = |j1 , m1 = j1 # ⊗ |j2 , m2 = j2 # ,

where Jmax = j1 + j2 .

2. From this state, we can use of the total spin lowering operator Jˆ− to
find all states with J = Jmax and mj = −Jmax · · · Jmax .

3. From the state with J = Jmax and mj = Jmax − 1, one can then obtain
the state with J = Jmax − 1 and mj = Jmax − 1 by orthogonality.6 Now
one can return to the second step of the programme and repeat until
J = |j1 − j2 | when all (2j1 + 1)(2j2 + 1) basis states have been obtained.

6.4.1 Addition of two spin 1/2 degrees of freedom

For two spin 1/2 degrees of freedom, we could simply construct and diagonalize
the complete 4 × 4 matrix elements of the total spin. However, to gain some
intuition for the general case, let us consider the programme above. Firstly,
the maximal total spin state is given by

|S = 1, mS = 1, s1 = 1/2, s2 = 1/2# = |s1 = 1/2, ms1 = 1/2# ⊗ |s2 = 1/2, ms2 = 1/2# .

Now, since s1 = 1/2 and s = 1/2 is implicit, we can rewrite this equation in a
more colloquial form as

|S = 1, mS = 1# = | ↑1 # ⊗ | ↑2 # .

We now follow step 2 of the programme and subject the maximal spin state
to the total spin lowering operator, Ŝ− = Ŝ1− + Ŝ1+ . In doing so, making use
of Eq. (4.5), we find
√
Ŝ− |S = 1, mS = 1# = 2!|S = 1, mS = 0# = ! (| ↓1 # ⊗ | ↑2 # + | ↑1 # ⊗ | ↓2 #) ,
5
In fact, one may show that the general matrix element is given by
s
(j1 + j2 − j)!(j + j1 − j2 )!(j + j2 − j1 )!(2j + 1)
$j1 , m1 , j2 , m2 |j, mj , j1 , j2 % = δmj ,m1 +m2
(j + j1 + j2 + 1)!
p
X (−1)k (j1 + m1 )!(j1 − m1 )!(j2 + m2 )!(j2 − m2 )!(j + m)!(j − m)!
× .
k!(j1 + j2 − j − k)!(j1 − m1 − k)!(j2 + m2 − k)!(j − j2 + m1 + k)!(j − j1 − m2 + k)!
k

6
Alternatively, as a maximal spin state, |J = Jmax − 1, mj = Jmax − 1, j1 , j2 % can be
identified by the “killing” action of the raising operator, Jˆ+ .

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6.4. ADDITION OF ANGULAR MOMENTA 60

i.e. |S = 1, mS = 0# = √1 (|
2
↓1 # ⊗ | ↑2 # + | ↑1 # ⊗ | ↓2 #). Similarly,
√ √
Ŝ− |S = 1, mS = 0# = 2!|S = 1, mS = −1# = 2!| ↓1 # ⊗ | ↓2 # ,

i.e. |S = 1, mS = −1# = | ↓1 # ⊗ | ↓2 #. This completes the construction of

the manifold of spin S = 1 states – the spin triplet states. Following the
programme, we must now consider the lower spin state.
In this case, the next multiplet is the unique total spin singlet state
|S = 0, mS = 0#. The latter must be orthogonal to the spin triplet state
|S = 1, mS = 0#. As a result, we can deduce that
1
|S = 0, mS = 0# = √ (| ↓1 # ⊗ | ↑2 # − | ↑1 # ⊗ | ↓2 #) .
2

6.4.2 Addition of angular momentum and spin

We now turn to the problem of the addition of angular momentum and spin,
Ĵ = L̂ + Ŝ. In the original basis, for a given angular momentum ", one can
identify 2 × (2" + 1) product states |", m% # ⊗ | ↑# and |", m% # ⊗ | ↓#, with
m% = −", · · · ", involving eigenstates of L̂2 , L̂z , Ŝ2 and Ŝz , but not Ĵ2 . From
these basis states, we are looking for eigenstates of Ĵ2 , Jˆz , L̂2 and Ŝ2 . To
undertake this programme, it is helpful to recall the action of the angular
momentum raising and lower operators,

L̂± |", m% # = ((" ± m% + 1)(" ∓ m% ))1/2 !|", m% ± 1# ,

as well as the identity

2L̂ · Ŝ
' () *
Ĵ = L̂ + Ŝ + 2L̂z Ŝz + L̂+ Ŝ− + Ŝ+ L̂− .
2 2 2

For the eigenstates of Ĵ2 , Jˆz , L̂2 and Ŝ2 we will adopt the notation |j, mj , "#
leaving the spin S = 1/2 implicit. The maximal spin state is given by7

|" + 1/2, " + 1/2, "# = |", "# ⊗ | ↑# .

To obtain the remaining states in the multiplet, |j = " + 1/2, mj=%+1/2 , "#, we
may simply apply the total spin lowering operator Jˆ− ,

Jˆ− |", "# ⊗ | ↑# = !(2")1/2 |", " − 1# ⊗ | ↑# + !|", "# ⊗ | ↓# .

Normalising the right-hand side of this expression, one obtains the spin state,
+ +
2" 1
|" + 1/2, " − 1/2, "# = |", " − 1# ⊗ | ↑# + |", "# ⊗ | ↓# .
2" + 1 2" + 1
7
The proof runs as follows:

Jˆz |$, $% ⊗ | ↑% = (L̂z + Ŝz )|$, $% ⊗ | ↑% = ($ + 1/2)!|$, $% ⊗ | ↑% ,

and
1
Ĵ2 |$, $% ⊗ | ↑% = !2 ($($ + 1) + 1/2(1/2 + 1) + 2$ )|$, $% ⊗ | ↑%
2
= !2 ($ + 1/2)($ + 3/2)|$, $% ⊗ | ↑% .

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6.4. ADDITION OF ANGULAR MOMENTA 61

By repeating this programme, one can develop an expression for the full
set of basis states,
+
" + mj + 1/2
|j = " + 1/2, mj , "# = |", mj − 1/2# ⊗ | ↑#
2" + 1
+
" − mj + 1/2
+ |", mj + 1/2# ⊗ | ↓# ,
2" + 1
with mj = " + 1/2, · · · , −(" + 1/2). In order to obtain the remaining states
with j = " − 1/2, we may look for states with mj = " − 1/2, · · · , −(" − 1/2)
which are orthogonal to |" + 1/2, mj , "#. Doing so, we obtain
+
" − mj + 1/2
|" − 1/2, mj , "# = − |", mj − 1/2# ⊗ | ↑#
2" + 1
+
" + mj + 1/2
+ |", mj + 1/2# ⊗ | ↓# .
2" + 1
Finally, these states can be cast in a compact form by setting

|j = " ± 1/2, mj , "# = α± |", mj − 1/2# ⊗ | ↑# + β± |", mj + 1/2# ⊗ | ↓# , (6.2)

,
%±mj +1/2
where α± = ± 2%+1 = ±β∓ .

6.4.3 Addition of two angular momenta J = 1

As mentioned above, for the general case the programme is algebraically tech-
nical and unrewarding. However, for completeness, we consider here the ex-
plicit example of the addition of two spin 1 degrees of freedom. Once again,
the maximal spin state is given by

|J = 2, mJ = 2, j1 = 1, j2 = 1# = |j1 = 1, m1 = 1# ⊗ |j2 = 1, m2 = 1# ,

or, more concisely, |2, 2# = |1# ⊗ |1#, where we leave j1 and j2 implicit. Once
again, making use of Eq. (4.5) and an ecomony of notation, we find (exercise)


 |2, 2# = |1# ⊗ |1#


 |2, 1# = 2 (|0# ⊗ |1# + |1# ⊗ |0#)
 √1

|2, 0# = √16 (| − 1# ⊗ |1# + 2|0# ⊗ |0# + |1# ⊗ | − 1#) .




 |2, −1# = √12 (|0# ⊗ | − 1# + | − 1# ⊗ |0#)


|2, 2# = | − 1# ⊗ | − 1#

Then, from the expression for |2, 1#, we can construct the next maximal spin
state |1, 1# = √12 (|0# ⊗ |1# − |1# ⊗ |0#), from the orthogonality condition. Once
again, acting on this state with the total spin lowering operator, we obtain the
remaining members of the multiplet,

 |1, 1# = 2 (|0# ⊗ |1# − |1# ⊗ |0#)
 √1

|1, 0# = √12 (| − 1# ⊗ |1# − |1# ⊗ | − 1#) .


 |1, −1# = √1 (| − 1# ⊗ |0# − |0# ⊗ | − 1#)
2

Finally, finding the state orthogonal to |1, 0# and |2, 0#, we obtain the final
state,
1
|0, 0# = √ (| − 1# ⊗ |1# − |0# ⊗ |0# + |1# ⊗ | − 1#) .
3

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Chapter 7

Approximation methods for

stationary states

7.1 Time-independent perturbation theory

While we have succeeded in deriving formal analytical solutions for stationary
states of the Schrödinger operator in a variety of settings, in the majority of
practical applications, exact solutions are inaccessible.1 For example, if an
atom is placed in an external electric field, the energy levels shift, and the
wavefunctions become distorted — the Stark effect. The new energy levels
and wavefunctions could in principle be obtained by writing down a complete
Hamiltonian, including the external field. Indeed, such a programme may
be achieved for the hydrogen atom. But even there, if the external field is
small compared with the electric field inside the atom (which is billions of
volts per meter) it is easier to compute the changes in the energy levels and
wavefunctions within a scheme of successive corrections to the zero-field values.
This method, termed perturbation theory, is the single most important method
for solving problems in quantum mechanics, and is widely used in atomic
physics, condensed matter and particle physics.

! Info. It should be acknowledged that there are – typically very interesting

– problems which cannot be solved using perturbation theory, even when the per-
turbation is very weak; although such problems are the exception rather than the
rule. One such case is the one-dimensional problem of free particles perturbed by
a localized potential of strength λ. As we found earlier in chapter 2, switching on
an arbitrarily weak attractive potential causes the k = 0 free particle wavefunction
to drop below the continuum of plane wave energies and become a localized bound
state with binding energy of order λ2 . However, on changing the sign of λ to give a
repulsive potential, there is no bound state; the lowest energy plane wave state stays
at energy zero. Therefore the energy shift on switching on the perturbation cannot
be represented as a power series in λ, the strength of the perturbation. This partic-
ular difficulty does not typically occur in three dimensions, where arbitrarily weak
potentials do not in general lead to bound states.

! Exercise. Focusing on the problem of bound state formation in one-dimension

described above, explore the dependence of the ground state energy on λ. Consider
why a perturbative expansion in λ is infeasible.

1
Indeed, even if such a solution is formally accessible, its complexity may render it of no
practical benefit.

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7.1. TIME-INDEPENDENT PERTURBATION THEORY 63

7.1.1 The Perturbation Series

Let us then consider an unperturbed Hamiltonian, Ĥ (0) , having known eigen-
(0)
states |n(0) ! and eigenvalues En ,

Ĥ (0) |n(0) ! = En(0) |n(0) ! . (7.1)

In the following we will address the question of how the eigenstates and
eigenenergies are modified by the imposition of a small perturbation, Ĥ (1)
(such as that imposed by an external electric or magnetic field on a charged
particle, or the deformation of some other external potential). In short, we
are interested in the solution of the Schrödinger equation,

(Ĥ (0) + Ĥ (1) )|n! = En |n! . (7.2)

(0)
If the perturbation is small, "n(0) |Ĥ (1) |n(0) ! # En , it seems natural to
suppose that, on turning on Ĥ (1) , the eigenfunctions and eigenvalues will
change adiabatically from their unperturbed to their perturbed values, a sit-
uation described formally as “adiabatic continuity”,

|n(0) ! $−→ |n!, En(0) $−→ En .

However, note that this is not always the case. For example, as mentioned
above, an infinitesimal perturbation has the capacity to develop a bound state
not present in the unperturbed system. For now, let us proceed with the per-
turbative expansion and return later to discuss its potential range of validity.
The basic assumption that underpins the perturbation theory is that, for
Ĥ (1) small, the leading corrections are of the same order of magnitude as
Ĥ (1) itself. The perturbed eigenenergies and eigenvalues can then be ob-
tained to a greater accuracy by a successive series of corrections, each of order
"Ĥ (1) !/"Ĥ (0) ! compared with the previous. To identify terms of the same
order in "Ĥ (1) !/"Ĥ (0) !, it is convenient to extract from Ĥ (1) a dimensionless
parameter λ, characterising the relative magnitude of the perturbation against
Ĥ (0) , and then expand |n! and En as a power series in λ, i.e.
∞
!
|n! = |n(0) ! + λ|n(1) ! + λ2 |n(2) ! + · · · = λm |n(m) !,
m=0
∞
!
En = En(0) + λEn(1) + λ2 En(2) + · · · = λm En(m) .
m=0

One may think of the parameter λ as an artifical book-keeping device to or-

ganize the perturbative expansion, and which is eventually set to unity at the
end of the calculation.
Applied to the stationary form of the Schrödinger equation (7.2), an ex-
pansion of this sort leads to the relation

(Ĥ (0) + λĤ (1) )(|n(0) ! + λ|n(1) ! + λ2 |n(2) ! + · · ·)

= (En(0) + λEn(1) + λ2 En(2) + · · ·)(|n(0) ! + λ|n(1) ! + λ2 |n(2) ! + · · ·) .(7.3)

From this equation, we must relate terms of equal order in λ. At the lowest
order, O(λ0 ), we simply recover the unperturbed equation (7.1). In practical
applications, one is usually interested in determining the first non-zero per-
turbative correction. In the following, we will explore the form of the first and
second order perturbative corrections.

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7.1. TIME-INDEPENDENT PERTURBATION THEORY 64

7.1.2 First order perturbation theory

Isolating terms from (7.3) which are first order in λ,

Ĥ (0) |n(1) ! + Ĥ (1) |n(0) ! = En(0) |n(1) ! + En(1) |n(0) ! . (7.4)

and taking the inner product with the unperturbed states "n(0) |, one obtains

"n(0) |Ĥ (0) |n(1) ! + "n(0) |Ĥ (1) |n(0) ! = "n(0) |En(0) |n(1) ! + "n(0) |En(1) |n(0) ! .
(0)
Noting that "n(0) |Ĥ (0) = "n(0) |En , and exploiting the presumed normaliza-
tion "n(0) |n(0) ! = 1, one finds that the first order shift in energy is given
simply by the expectation value of the perturbation taken with respect to the
unperturbed eigenfunctions,

En(1) = "n(0) |Ĥ (1) |n(0) ! . (7.5)

Turning to the wavefuntion, if we instead take the inner product of (7.4)

with "m(0) | (with m '= n), we obtain

"m(0) |Ĥ (0) |n(1) ! + "m(0) |Ĥ (1) |n(0) ! = "m(0) |En(0) |n(1) ! + "m(0) |En(1) |n(0) ! .
(0)
Once again, with "m(0) |Ĥ (0) = "m(0) |Em and the orthogonality condition on
the wavefunctions, "m(0) |n(0) ! = 0, one obtains an expression for the first order
shift of the wavefunction expressed in the unperturbed basis,

"m(0) |Ĥ (1) |n(0) !

"m(0) |n(1) ! = (0) (0)
. (7.6)
En − Em

In summary, setting λ = 1, to first order in perturbation theory, we have

the eigenvalues and eigenfunctions,

En ( En(0) + "n(0) |Ĥ (1) |n(0) !

! "m(0) |Ĥ (1) |n(0) !
|n! ( |n(0) ! + |m(0) ! (0) (0)
.
m"=n En − Em

Before turning to the second order of perturbation theory, let us first consider
a simple application of the method.

! Example: Ground state energy of the Helium atom: For the Helium
atom, two electrons are bound to a nucleus of two protons and two neutrons. If
one neglects altogether the Coulomb interaction between the electrons, in the ground
state, both electrons would occupy the ground state hydrogenic wavefunction (scaled
appropriately to accommodate the doubling of the nuclear charge) and have opposite
spin. Treating the Coulomb interaction between electrons as a perturbation, one may
then use the basis above to estimate the shift in the ground state energy with

1 e2
Ĥ (1) = .
4π$0 |r1 − r2 |

As we have seen, the hydrogenic wave functions are specified by three quantum
numbers, n, %, and m. In the ground state, the corresponding wavefunction takes the
spatially isotropic form,
" #1/2
1
"r|n = 1, % = 0, m = 0! = ψ100 (r) = e−r/a , (7.7)
πa3

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7.1. TIME-INDEPENDENT PERTURBATION THEORY 65

2
0 !
where a = 4π"
Ze2 me = Z denotes the atomic Bohr radius for a nuclear charge Z.
a0

For the Helium atom (Z = 2), the symmetrized ground state of the unperturbed
Hamiltonian is then given by the spin singlet (S = 0) electron wavefunction,
1
|g.s.(0) ! = √ (|100, ↑! ⊗ |100, ↓! − |100, ↓! ⊗ |100, ↑!) .
2
Here we have used the direct product ⊗ to discriminate between the two electrons.
Then, applying the perturbation theory formula above (7.5), to first order in the
Coulomb interaction, the energy shift is given by
$
e2 1 e−2(r1 +r2 )/a e2 C0
En(1) = "g.s.(0) |Ĥ (1) |g.s.(0) ! = dr1 dr2 = ,
4π$0 (πa )3 2 |r1 − r2 | 4π$0 2a
% −(z1 +z2 )
where we have defined the dimensionless constant C0 = (4π) 1
2 dz1 dz1 e|z1 −z2 | . Then,
making use of the identity,
$
1 1 1
dΩ1 dΩ2 = ,
(4π) 2 |z1 − z2 | max(z1 , z2 )
where the integrations runs over the angular coordinates of the vectors z1 and z2 ,
%∞ %∞
and z1,2 = |z1,2 |, one finds that C0 = 2 0 dz1 z12 e−z1 z1 dz2 z2 e−z2 = 5/4. As a
2
result, noting that the Rydberg energy, Ry = 4π"e 1
0 2a0
, we obtain the first order
energy shift ∆E = 4 ZRy ( 34eV for Z = 2. This leads to a total ground state
5

energy of (2Z 2 − 54 Z) Ry = −5.5Ry ( −74.8eV compared to the experimental value

of −5.807Ry.

7.1.3 Second order perturbation theory

With the first order of perturbation theory in place, we now turn to consider
the influence of the second order terms in the perturbative expansion (7.3).
Isolating terms of order λ2 , we have
Ĥ (0) |n(2) ! + Ĥ (1) |n(1) ! = En(0) |n(2) ! + En(1) |n(1) ! + En(2) |n(0) ! .
As before, taking the inner product with "n(0) |, one obtains
"n(0) |Ĥ (0) |n(2) ! + "n(0) |Ĥ (1) |n(1) !
= "n(0) |En(0) |n(2) ! + "n(0) |En(1) |n(1) ! + "n(0) |En(2) |n(0) ! .
Noting that the first two terms on the left and right hand sides cancel, we are
left with the result
En(2) = "n(0) |Ĥ (1) |n(1) ! − En(1) "n(0) |n(1) ! .
Previously, we have made use of the normalization of the basis states,
|n(0) !. We have said nothing so far about the normalization of the exact
eigenstates, |n!. Of course, eventually, we would like to ensure normalization
of these states too. However, to facilitate the perturbative expansion, it is
operationally more convenient to impose a normalization on |n! through the
condition "n(0) |n! = 1. Substituting the λ expansion for |n!, we thus have
"n(0) |n! = 1 = "n(0) |n(0) ! + λ"n(0) |n(1) ! + λ2 "n(0) |n(2) ! + · · · .
From this relation, it follows that "n(0) |n(1) ! = "n(0) |n(2) ! = · · · = 0.2 We can
(1)
therefore drop the term En "n(0) |n(1) ! from consideration. As a result, we
2
Alternatively, would we suppose that |n! and |n(0) ! were both normalised to unity,
to leading order, |n! = |n(0) ! + |n(1) !, and "n(0) |n(1) ! + "n(1) |n(0) ! = 0, i.e. "n(0) |n(1) !
is pure imaginary. This means that if, to first order, |n! has a component parallel to
|n(0) !, that component has a small imaginary amplitude allowing us to define |n! =
eiφ |n(0) !+orthog. components. However, the corresponding phase factor φ can be eliminated
(1)
by redefining the phase of |n!. Once again, we can conclude that the term En "n(0) |n(1) !
can be eliminated from consideration.

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7.1. TIME-INDEPENDENT PERTURBATION THEORY 66

obtain
! "m(0) |Ĥ (1) |n(0) !
En(2) = "n(0) |Ĥ (1) |n(1) ! = "n(0) |Ĥ (1) |m(0) ! (0) (0)
,
m"=n En − Em
i.e.
! |"m(0) |Ĥ (1) |n(0) !|2
En(2) = (0) (0)
. (7.8)
m"=n En − Em

From this result, we can conclude that,

! for the ground state, the second order shift in energy is always negative;
! if the matrix elements of Ĥ (1) are of comparable magnitude, neighbour-
ing levels make a larger contribution than distant levels;
! Levels that lie in close proximity tend to be repelled;
! If a fraction of the states belong to a continuum, the sum in Eq. (7.8)
should be replaced by an intergral.
Once again, to illustrate the utility of the perturbative expansion, let us con-
sider a concrete physical example.

! Example: The Quadratic Stark Effect: Consider the influence of an exter-

nal electric field on the ground state of the hydrogen atom. As the composite electron
and proton are drawn in different directions by the field, the relative displacement
of the electon cloud and nucleus results in the formation of a dipole which serves to
lower the overall energy. In this case, the perturbation due to the external field takes
the form
Ĥ (1) = qEz = qEr cos θ ,
where q = −|e| denotes the electron charge, and the electric field, E = Eêz is oriented
(0) (0)
along the z-axis. With the non-perturbed energy spectrum given by En#m ≡ En =
(0)
−Ry/n2 , the ground state energy is given by E (0) ≡ E100 = −Ry. At first order
in the electric field strength, E, the shift in the ground state energy is given by
E (1) = "100|qEz|100! where the ground state wavefunction was defined above (7.7).
Since the potential perturbation is antisymmetric in z, it is easy to see that the energy
shift vanishes at this order.
We are therefore led to consider the contribution second order in the field strength.
Making use of Eq. (7.8), and neglecting the contribution to the energy shift from the
continuum of unbound positive energy states, we have
! |"n%m|eEz|100!|2
E (2) = (0) (0)
,
n#=1,#,m E1 − En

where |n%m! denote the set of bound state hydrogenic wavefunctions. Although the
expression for E (2) can be computed exactly, the programme is somewhat tedious.
However, we can place a strong bound on the energy shift through the following
(0) (0) (0) (0)
argument: Since, for n > 2, |E1 − En | > |E1 − E2 |, we have
1 !
|E (2) | < (0) (0)
"100|eEz|n%m!"n%m|eEz|100! .
E2 − E1 n#=1,#,m
& &
Since n,#,m |n%m!"n%m| = I, we have n#=1,#,m |n%m!"n%m| = I−|100!"100|. Finally,
since "100|z|100! = 0, we can conclude that |E (2) | < (0) 1 (0) "100|(eEz)2 |100!. With
E2 −E1
(0) 2 (0) (0)
"100|z 2 |100! = a20 , E1 = − 4π"
e 1
0 2a0
= −Ry, and E2 = E1 /4, we have
1 8
|E (2) | < (eE)2 a20 = 4π$0 E 2 a30 .
3 2
4 e /8π$ a
0 0 3

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7.2. DEGENERATE PERTURBATION THEORY 67

Furthermore, since all terms in the perturbation series for E (2) are negative, the first
2
term in the series sets a lower bound, |E (2) | > |$210|eEz|100%|
(0) (0) . From this result, one
E2 −E1
can show that 0.55 × 83 4π$0 E 2 a30 < |E (2) | < 83 4π$0 E 2 a30 (exercise).3

7.2 Degenerate perturbation theory

The perturbative analysis above is reliable providing that the successive terms
in the expansion form a convergent series. A necessary condition is that the
matrix elements of the perturbing Hamiltonian must be smaller than the cor-
responding energy level differences of the original Hamiltonian. If it has dif-
ferent states with the same energy (i.e. degeneracies), and the perturbation
has non-zero matrix elements between these degenerate levels, then obviously
the theory breaks down. However, the problem is easily fixed. To understand
how, let us consider a particular example.
p̂2
Recall that, for the simple harmonic oscillator, Ĥ = 2m + 12 mω 2 x2 , the
2
ground state wavefunction is given by "x|0! = ( mω π! )
1/4 e−ξ /2 , where ξ =
' 4mω 1/4 −ξ 2 /2
x mω/! and the first excited state by "x|1! = ( π! ) ξe . The wave-
functions for the two-dimensional harmonic oscillator,
1 2 1
Ĥ (0) = (p̂ + p̂2y ) + mω 2 (x2 + y 2 ) .
2m x 2
are given simply by the product of two one-dimensional oscillators. So, setting
' ( )1/2 −(ξ2 +η2 )/2
η = y mω/!, the ground state is given by "x, y|0, 0! = mω π! e ,
and the two degenerate first excited states, an energy !ω above the ground
state, are given by,
* + mω ,1/2 *
"x, y|1, 0! −(ξ 2 +η 2 )/2 ξ
= e .
"x, y|0, 1! π! η
Suppose now we add to the Hamiltonian a perturbation,
Ĥ (1) = αmω 2 xy = α!ωξη ,
controlled by a small parameter α. Notice that, by symmetry, the following
matrix elements all vanish, "0, 0|Ĥ (1) |0, 0! = "1, 0|Ĥ (1) |1, 0! = "0, 1|Ĥ (1) |0, 1! =
0. Therefore, according to a naı̈ve perturbation theory, there is no first-order
correction to the energies of these states. However, on proceeding to consider
the second-order correction to the energy, the theory breaks down. The off-
diagonal matrix element, "1, 0|Ĥ (1) |0, 1! = 0 is non-zero, but the two states
|0, 1! and |1, 0! have the same energy! This gives an infinite term in the series
(2)
for En=1 .
Yet we know that a small perturbation of this type will not wreck a two-
dimensional simple harmonic oscillator – so what is wrong with our approach?
To understand the origin of the problem and its fix, it is helpful to plot the
original harmonic oscillator potential 12 mω 2 (x2 + y 2 ) together with the per-
turbing potential αmω 2 xy. The first of course has circular symmetry, the
second has two symmetry axes oriented in the directions x = ±y, climbing
most steeply from the origin along x = y, falling most rapidly in the directions
x = y. If we combine the two potentials into a single quadratic form,
- " #2 " #2 .
1 1 x + y x − y
mω 2 (x2 + y 2 ) + αmω 2 xy = mω 2 (1 + α) √ + (1 − α) √ .
2 2 2 2
3
Energetic readers might like to contemplate how the exact answer of |E (2) | = 94 E 2 a30 can
be found exactly. The method can be found in the text by Shankar.

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7.2. DEGENERATE PERTURBATION THEORY 68

the original circles of constant potential become ellipses, with their axes aligned
along x = ±y.
As soon as the perturbation is introduced, the eigenstates lie in the direc-
tion of the new elliptic axes. This is a large change from the original x and
y bases, which is not proportional to the small parameter α. But the origi-
nal unperturbed problem had circular symmetry, and there was no particular
reason to choose the x and y axes as we did. If we had instead chosen as
our original axes the lines x = ±y, the basis states would not have undergone
large changes on switching on the perturbation. The resolution of the problem
is now clear: Before switching on the perturbation, one must choose a set of
basis states in a degenerate subspace in which the perturbation is diagonal.
In fact, for the simple harmonic oscillator example above, the problem can
of course be solved exactly √ by rearranging the coordinates to lie along the
symmetry axes, (x ± y)/ 2. It is then clear that, despite the results of naı̈ve
first order perturbation
√ theory, there is indeed a first order shift in the energy
levels, !ω → !ω 1 ± α ≈ !ω(1 ± α/2).

! Example: Linear Stark Effect: As with the two-dimensional harmonic

oscillator discussed above, the hydrogen atom has a non-degenerate ground state, but
degeneracy in its lowest excited states. Specifically, there are four n = 2 states, all
having energy − 14 Ry. In spherical coordinates, these wavefunctions are given by
  + ,
 ψ200 (r) " #1/2 
 2 − ar0
1
ψ210 (r) = e−r/2a0
 ar0 cos
r
θ .
 32πa30 
ψ21,±1 (r) ±iφ
sin θ
a0 e

When perturbing this system with an electric field oriented in the z-direction, Ĥ (1) =
qEr cos θ, a naı̈ve application of perturbation theory predicts no first-order shift in
any of these energy levels. However, at second order in E, there is a non-zero matrix
element between two degenerate levels ∆ = "200|Ĥ (1) |210!. All the other matrix
elements between these basis states in the four-dimensional degenerate subspace are
zero. So the only diagonalization necessary is within the two-dimensional degenerate
subspace spanned by |200! and |210!, i.e.
" #
0 ∆
Ĥ =
(1)
,
∆ 0
+ ,% + ,+ ,2
with ∆ = qE 1
32πa30
2− r
a0
r cos θ
a0 e−r/a0 r2 dr sin θ dθ dφ = −3qEa0 .
Diagonalizing Ĥ (1) within this sub-space, the new basis states are given by the
√
symmetric and antisymmetric combinations, (|200! ±| 210!)/ 2 with energy shifts
±∆, linear in the perturbing electric field. The states |2%, ±1! are not changed by
the presence of the field to this level of approximation, so the complete energy map
of the n = 2 states in the electric field has two states at the original energy of −Ry/4,
one state moved up from that energy by ∆, and one down by ∆. Notice that the new
√
eigenstates (|200! ±| 210!)/ 2 are not eigenstates of the parity operator -- a sketch
of their wavefunctions reveals that, in fact, they have non-vanishing electric dipole
moment µ. Indeed this is the reason for the energy shift, ±∆ = ∓2eEa0 = ∓µ · E.

! Example: As a second and important example of the degenerate perturbation

theory, let us consider the problem of a particle moving in one dimension and subject
to a weak periodic potential, V (x) = 2V cos(2πx/a) – the nearly free electron
model. This problem provides a caricature of a simple crystalline solid in which
(free) conduction electrons propagate in the presence of a periodic background lattice
potential. Here we suppose that the strength of the potential V is small as compared
to the typical energy scale of the particle so that it may be treated as a small pertur-

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7.3. VARIATIONAL METHOD 69

bation. In the following, we will suppose that the total one-dimensional system is of
length L = N a, with periodic boundary conditions.
For the unperturbed free particle system, the eigenstates are simply plane waves
ψk (x) = "x|k! = √1L eikx indexed by the wavenumber k = 2πn/L, n integer, and
(0)
the unperturbed spectrum is given by Ek = !2 k 2 /2m. The matrix elements of the
perturbation between states of different wavevector are given by
$
1 L "
"k|V |k ! =
'
dxei(k −k)x 2V cos(2πx/a)
L 0
$ L+ ,
V " "
= ei(k −k+2π/a)x + ei(k −k−2π/a)x = V δk" −k,±2π/a .
L 0

Note that all diagonal matrix elements of the perturbation are identically zero. In
general, for wavevectors k and k ' separated by G = 2π/a, the unperturbed states are
non-degenerate. For these states one can compute the relative energy shift within
the framework of second order perturbation theory. However, for states k = −k ' =
G/2 ≡ π/a, the unperturbed free particle spectrum is degenerate. Here, and in
the neighbourhood of these k values, we must implement a degenerate perturbation
theory.
For the sinusoidal potential considered here, only states separated by G = 2π/a
are coupled by the perturbation. We may therefore consider matrix elements of the
full Hamiltonian between pairs of coupled states, |k = G/2 + q! and |k = −G/2 + q!
3 (0) 4
EG/2+q V
H= (0) .
V E−G/2+q

As a result, to leading order in V , we obtain the eigenvalues,

" #1/2
!2 2 π 2 !4 q 2
Eq = (q + (π/a)2 ) ± V 2 + .
2m 4m2 a2

In particular, this result shows that, for k = ±G/2, the degeneracy of the free particle
system is lifted by the potential. In the vicinity, |q| # G, the spectrum of eigenvalues
is separated by a gap of size 2V . The appearance of the gap mirrors the behaviour
found in our study of the Kronig-Penney model of a crystal studied in section 2.2.3.
The appearance of the gap has important consequences in theory of solids. Elec-
trons are fermions and have to obey Pauli’s exclusion principle. In a metal, at low
temperatures, electrons occupy the free particle-like states up to some (Fermi) energy
which lies away from gap. Here, the accessibility of very low-energy excitations due
to the continuum of nearby states allows current to flow when a small electric field is
applied. However, when the Fermi energy lies in the gap created by the lattice po-
tential, an electric field is unable to create excitations and induce current flow. Such
systems are described as (band) insulators.

7.3 Variational method

So far, in devising approximation methods for quantum mechanics, we have
focused on the development of a perturbative expansion scheme in which the
states of the non-perturbed system provided a suitable platform. Here, by
suitable, we refer to situations in which the states of the unperturbed system
mirror those of the full system – adiabatic contunity. For example, the states
of the harmonic oscillator potential with a small perturbation will mirror those
of the unperturbed Hamiltonian: The ground state will be nodeless, the first
excited state will be antisymmetric having one node, and so on. However, often
we working with systems where the true eigenstates of the problem may not
be adiabatically connected to some simple unperturbed reference state. This

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7.3. VARIATIONAL METHOD 70

situation is particularly significant in strongly interacting quantum systems

where many-particle correlations can effect phase transitions to new states
of matter – e.g. the development of superfluid condensates, or the fractional
quantum Hall fluid. To address such systems if it is often extremely effective to
“guess” and then optimize a trial wavefunction. The method of optimization
relies upon a simple theoretical framework known as the variational approach.
For reasons that will become clear, the variational method is particularly well-
suited to addressing the ground state.
The variational method involves the optimization of some trial wavefunc-
tion on the basis of one or more adjustable parameters. The optimization
is achieved by minimizing the expectation value of the energy on the trial
function, and thereby finding the best approximation to the true ground state
wave function. This seemingly crude approach can, in fact, give a surprisingly
good approximation to the ground state energy but, it is usually not so good
for the wavefunction, as will become clear. However, as mentioned above,
the real strength of the variational method arises in the study of many-body
quantum systems, where states are more strongly constrained by fundamental
symmetries such as “exclusion statistics”.
To develop the method, we’ll begin with the problem of a single quantum
p̂2
particle confined to a potential, Ĥ = 2m + V (r). If the particle is restricted to
one dimension, and we’re looking for the ground state in any fairly localized
potential well, it makes sense to start with a trial wavefunction which belongs
2
to the family of normalized Gaussians, |ψ(α)! = (α/π)1/4 e−αx /2 . Such a trial
state fulfils the criterion of being nodeless, and is exponentially localized to
the region of the binding potential. It also has the feature that it includes the
exact ground states of the harmonic binding potential.
The variation approach involves simply minimizing the expectaton value of
the energy, E = "ψ(α)|Ĥ|ψ(α)!, with respect to variations of the variational
parameter, α. (Of course, as with any minimization, one must check that the
variation does not lead to a maximum of the energy!) Not surprisingly, this
programme leads to the exact ground state for the simple harmonic oscillator
potential, while it serves only as an approximation for other potentials. What
is perhaps surprising is that the result is only off by only ca. 30% or so
for the attractive δ-function potential, even though the wavefunction looks
substantially different. Obviously, the Gaussian family cannot be used if there
is an infinite wall anywhere: one must find a family of wavefunctions vanishing
at such a boundary.

! Exercise. Using the Gaussian trial state, find the optimal value of the varia-
tional state energy, E, for an attractive δ-function potential and compare it with the
exact result.

To gain some further insight into the approach, suppose the Hamiltonian
Ĥ has a set of eigenstates, Ĥ|n! = En |n!. Since the Hamiltonian is Her-
mitian, these states span the space of possible wave functions,
& including our
variational family of Gaussians, so we can write, |ψ(α)! = n an (α)|n!. From
this expansion, we have

"ψ(α)|Ĥ|ψ(α)! !
= |an |2 En ≥ E0 ,
"ψ(α)|ψ(α)! n

for any |ψ(α)!. (We don’t need the denominator if we’ve chosen a family of
normalized wavefunctions, as we did with the Gaussians above.) Evidently,

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7.3. VARIATIONAL METHOD 71

minimizing the left hand side of this equation as function of α provides an

upper bound on the ground state energy.
We can see immediately that this will probably be better for finding the
ground state energy than for the wavefunction: Suppose the optimum state in
our family is given by, say, |αmin ! = N (|0!+0.2|1!) with the normalization N (
0.98, i.e. a 20% admixture of the first excited state. Then the wavefunction is
off by ca. 20%, but the energy estimate will be too high by only 0.04(E1 −E0 ),
usually a much smaller error.

! Example: To get some idea of of how well the variational approach works,
consider its application to the to the ground state of the hydrogen atom. Taking
into account the spherical symmetry of the ground state, we may focus on the one-
dimensional radial component of the wavefunction. Defining the trial radial wave-
function u(ρ) (presumed real), where ρ = r/a0 , the variational energy is given by
%∞ + 2 ,
0
dρ u(ρ) d
dρ2 + 2
ρ u(ρ)
E(u) = −Ry %∞ .
0
dρ u (ρ)
2

For the three families of trial functions,

ρ
u1 (ρ) = ρe−αρ , u2 (ρ) = , u3 (ρ) = ρ2 e−αρ ,
α 2 + ρ2
and finds αmin = 1, π/4, and 3/2 respectively (exercise). The first family, u1 , in-
cludes the exact result, and the minimization procedure correctly finds it. For the
three families, the predicted energy of the optimal state is off by 0, 25%, and 21%
respectively.
The corresponding error in the wavefunction is defined by how far the square of
the overlap with the true ground state wavefunction falls short of unity. For the three
families, ε = 1 − |"ψ0 |ψvar |2 = 0, 0.21, and 0.05. Notice here that our handwaving
argument that the energies would be found much more accurately than the wavefunc-
tions seems to come unstuck. The third family has far better wavefunction overlap
than the second, but only a slightly better energy estimate. Why? A key point is
that the potential is singular at the origin; there is a big contribution to the potential
energy from a rather small region, and the third family of trial states is the least
accurate of the three there. The second family of functions are very inaccurate at
large distances: the expectation value "r! = 1.5a0 , ∞, 1.66a0 for the three families.
But at large distances, both kinetic and potential energies are small, so the result can
still look reasonable. These examples reinforce the point that the variational method
should be implemented with some caution.

In some cases, one can exploit symmetry to address the properties of

higher-lying states. For example, if the one-dimensional attractive potential is
symmetric about the origin, and has more than one bound state, the ground
state will be even, the first excited state odd. Therefore, we can estimate the
energy of the first
√ excited state by minimizing a family of odd functions, such
π 1/2 −αx2 /2
as ψ(x, α) = ( 2α3/2 ) xe .

! Example: Helium atom addressed by the variational approach: For

the hydrogen atom, we know that the ground state energy is 1 Ry, or 13.6 eV. The
He+ ion (with just a single electron) has a nuclear charge of Z = 2, so the ground
state energy of the electron, being proportional to Z 2 , will now be equal to 4 Ry.
Therefore, for the He atom, if we neglect their mutual interaction, the electrons will
occupy the ground state wavefunction having opposite spin, leading to a total ground
state energy of 8 Ry or 109 eV. In practice, as we have seen earlier, the repulsion
between the electrons lowers ground state energy to 79 eV (see page 64).
To get a better estimate for the ground state energy, one can retain the form of
Z 3 1/2 −Zr/a0
the ionic wavefunction, ( πa3) e , but rather than setting the nuclear charge
0

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 72

Z = 2, leave it as a variational parameter. In other words, let us accommodate the

effects of electron-electron repulsion, which must “push” the wavefunctions to larger
radii, by keeping exactly the same wavefunction profile but lessening the effective
nuclear charge as reflected in the spread of the wavefunction from Z = 2 to Z < 2.
The precise value will be set by varying it to find the minimum total energy, including
the term from electron-electron repulsion.
To find the potential energy from the nuclear-electron interactions, we of course
must use the actual nuclear charge Z = 2, but impose a variable Z for the wavefunc-
tion, so the nuclear potential energy for the two electrons is given by,
$ ∞
2e2 Z 3 e−2Zr/a0 e2
p.e. = −2 × 4πr2 dr 3 = −Z = −8Z Ry.
4π$0 0 πa0 r π$0 a0

This could have been inferred from the formula for the one electron ion, where the
potential energy for the one electron is −2Z 2 Ry, one factor of Z being from the
nuclear charge, the other from the consequent shrinking of the orbit. The kinetic
energy is even easier to determine: it depends entirely on the form of the wavefunction,
and not on the actual nuclear charge. So for our trial wavefunction it has to be Z 2 Ry
per electron. Finally, making use of our calculation on page 64, we can immediately Léon Nicolas Brillouin 1889-
write down the positive contribution to the energy expectation value from the electron- 1969
electron interaction, A French physi-
cis, his father,
$ Marcel Brillouin,
e2 Z3 e−2Z(r1 +r2 )/a0 5 e2 Z 5 grandfather,
dr1 dr2 = = Z Ry .
4π$0 (πa0 )
3 2 |r1 − r2 | 4 4π$0 2a0 4 Éleuthère Mas-
cart, and great-
Collecting all of the terms, the total variational state energy is given by: grandfather,
Charles Briot,
" # were physicists
5
E = −2 4Z − Z − Z Ry .
2 as well. He made
8 contributions to quantum mechanics,
radio wave propagation in the
Minimization of this energy with respect to Z obtains the minimum at Z = 2 − 16 5
, atmosphere, solid state physics, and
information theory.
leading to an energy of 77.5 eV. This result departs from the true value by about 1 eV.
So, indeed, the presence of the other electron leads effectively to a shielding of the Hendrik Anthony “Hans”
nuclear charge by an amount of ca. (5/16)e. Kramers 1894-1952
A Dutch
physicist who
This completes our discussion of the principles of the variational approach. conducted early
and important
However, later in the course, we will find the variational methods appearing in work in quantum
several important applications. Finally, to close this section on approximation theory and
methods for stationary states, we turn now to consider a framework which electromagnetic
dispersion rela-
makes explicit the connection between the quantum and classical theory in tions, solid-state
the limit ! → 0. physics, and
statistical mechanics. He was a
long-time assistant and friend to
Niels Bohr, and collaborated with
7.4 Wentzel, Kramers and Brillouin (WKB) method him on a 1924 paper contending
that light consists of probability
waves, which became a foundation of
The WKB (or Wentzel, Kramers and Brillouin) approximation describes a quantum mechanics. He introduced
“quasi-classical” method for solving the one-dimensional time-independent the idea of renormalization, a cor-
Schrödinger equation. Note that the consideration of one-dimensional systems nerstone of modern field theory, and
determined the dispersion formulae
is less restrictive that it may sound as many symmetrical higher-dimensional that led to Werner Heisenberg’s
problems are rendered effectively one-dimensional (e.g. the radial equation for matrix mechanics. He is not as well
known as some of his contemporaries
the hydrogen atom). The WKB method is named after physicists Wentzel, (primarily because his work was not
Kramers and Brillouin, who all developed the approach independently in widely translated into English), but
his name is still invoked by physicists
1926.4 Earlier, in 1923, the mathematician Harold Jeffreys had developed as they discuss Kramers dispersion
a general method of approximating the general class of linear, second-order theory, Kramers-Heisenberg dis-
persion formulae, Kramers opacity
4 formula, Kramers degeneracy, or
L. Brillouin, (1926). “La mcanique ondulatoire de Schrödinger: une mt́hode générale
de resolution par approximations successives”, Comptes Rendus de l’Academie des Sciences Kramers-Kronig relations.
183: 2426; H. A. Kramers, (1926). “Wellenmechanik und halbzählige Quantisierung”, Z.
Phys. 39: 828840; G. Wentzel (1926). “Eine Verallgemeinerung der Quantenbedingungen
für die Zwecke der Wellenmechanik”. Z. Phys. 38: 518529.

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 73

differential equations, which of course includes the Schrödinger equation.5 But

since the Schrödinger equation was developed two years later, and Wentzel,
Kramers, and Brillouin were apparently unaware of this earlier work, the con-
tribution of Jeffreys is often neglected.
The WKB method is important both as a practical means of approximat-
ing solutions to the Schrödinger equation, and also as a conceptual framework
for understanding the classical limit of quantum mechanics. The WKB ap-
proximation is valid whenever the wavelength, λ, is small in comparison to
other relevant length scales in the problem. This condition is not restricted
to quantum mechanics, but rather can be applied to any wave-like system
(such as fluids, electromagnetic waves, etc.), where it leads to approximation
schemes which are mathematically very similar to the WKB method in quan-
tum mechanics. For example, in optics the approach is called the eikonal
method, and in general the method is referred to as short wavelength
asymptotics. Whatever the name, the method is an old one, which predates
quantum mechanics – indeed, it was apparently first used by Liouville and
Green in the first half of the nineteenth century. In quantum mechanics, λ is
interpreted as the de Broglie wavelength, and L is normally the length scale of
the potential. Thus, the WKB method is valid if the wavefunction oscillates
many times before the potential energy changes significantly.

7.4.1 Semi-classical approximation to leading order

Consider then the propagation of a quantum particle in a slowly-varying one-
dimensional potential, V (x). Here, by “slowly-varying” we mean that, in any
small region the wavefunction is well-approximated by a plane wave, and that
the wavelength only changes over distances that are long compared with the
local value of the wavelength. We’re also assuming for the moment that the
particle has positive kinetic energy in the region. Under these conditions, we
can anticipate that the solution to the time-independent Schrödinger equation

!2 2
− ∂ ψ(x) + V (x)ψ(x) = Eψ(x) ,
2m x

will take the form A(x)e±ip(x)x/! where p(x) is the “local” value of the momen-
tum set by the classical value, p2 /2m + V (x) = E, and the amplitude, A(x), is
slowly-varying compared with the phase factor. Clearly this is a semi-classical
limit: ! has to be sufficiently small that there are many oscillations in the typ-
ical distance over which the potential varies.6
To develop this idea a little more rigorously, and to emphasize the rapid
phase variation in the semi-classical limit, we can parameterize the wavefunc-
tion as

ψ(x) = eiσ(x)/! .
5
H. Jeffreys, (1924). “On certain approximate solutions of linear differential equations of
the second order”, Proc. Lon. Math. Soc. 23: 428436.
6
To avoid any point of confusion, it is of course true that ! is a fundamental constant – not
easily adjusted! So what do we mean when we say that the semi-classical limit translates to
! → 0? The validity of the semi-classical approximation relies upon λ/L $ 1. Following the
de Broglie relation, we may write this inequality as h/pL $ 1, where p denotes the particle
momentum. Now, in this correspondence, both p and L can be considered as “classical”
scales. So, formally, we can think of think of accessing the semi-classical limit by adjusting
! so that it is small enough to fulfil this inequality. Alternatively, at fixed !, we can access
the semi-classical regime by reaching to higher and higher energy scales (larger and larger
p) so that the inequality becomes valid.

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 74

Here the complex function σ(x) encompasses both the amplitude and phase.
Then, with −!2 ∂x2 ψ(x) = −i!eiσ(x)/!∂x2 σ(x) + eiσ(x)/!(∂x σ)2 , the Schrödinger
equation may be rewritten in terms of the phase function as,

−i!∂x2 σ(x) + (∂x σ)2 = p2 (x) . (7.9)

Now, since we’re assuming the system is semi-classical, it makes sense to

expand σ(x) as a power series in ! setting,

σ = σ0 + (!/i)σ1 + (!/i)2 σ2 + · · · .

At the leading (zeroth) order of the expansion, we can drop the first term
in'(7.9), leading to (∂x σ0 )2 = p2 (x). Fixing the sign of p(x) by p(x) =
+ 2m(E − V (x)), we conclude that
$
σ0 (x) = ± p(x)dx .

For free particle systems – those for which the kinetic energy is proportional
to p2 – this expression coincides with the classical action.
From the form of the Schrödinger equation (7.9), it is evident that this ap-
proximate solution is only valid if we can ignore the first term. More precisely,
we must have
5 5
5 !∂x2 σ(x) 5
5 5
5 (∂x σ(x))2 5 ≡ |∂x (!/∂x σ)| # 1 .

But, in the leading approximation, ∂x σ ( p(x) and p(x) = 2π!/λ(x), so the

condition translates to the relation
1
|∂x λ(x)| # 1 .
2π
This means that the change in wavelength over a distance of one wavelength
must be small. Obviously, this condition can not always be met: In partic-
ular, if the particle is confined by an attractive potential, at the edge of the
classically allowed region, where E = V (x), p(x) must is zero and the corre-
sponding wavelength infinite. The approximation is only valid well away from
these classical turning points, a matter to which we will return shortly.

7.4.2 Next to leading order correction

Let us now turn to the next term in the expansion in !. Retaining terms from
Eq. (7.9) which are of order !, we have

−i!∂x2 σ0 + 2∂x σ0 (!/i)∂x σ1 = 0 .

Rearranging this equation, and integrating, we find

∂x2 σ0 ∂x p 1
∂x σ1 = − =− , σ1 (x) = − ln p(x) .
2∂x σ0 2p 2
So, to this order of approximation, the wavefunction takes the form,
C1 (i/!) R p dx C2 −(i/!) R p dx
ψ(x) = ' e +' e , (7.10)
p(x) p(x)

where C1 and C2 denote constants of integration. To interpret the factors of

'
p(x), consider the first term: a wave moving to the right. Since p(x) is real

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 75

(remember we are currently considering the classically allowed region where

E > V (x)), the exponential has modulus unity, and the local probability den-
sity is proportional to 1/p(x), i.e. to 1/v(x), where v(x) denotes the velocity
of the particle. This dependence has a simple physical interpretation: The
probability of finding the particle in any given small interval is proportional
to the time it spends there. Hence it is inversely proportional to its speed.
We turn now to consider the wavefunction in the classically forbidden
region where

p2 (x)
= E − V (x) < 0 .
2m
Here p(x) is of course pure imaginary, but the same formal phase solution of the
Schrödinger equation applies provided, again, that the particle is remote from
the classical turning points where E = V (x). In this region, the wavefunction
takes the general form,

C1% R C% R
ψ(x) = ' e−(1/!) |p| dx
+ ' 2 e(1/!) |p| dx . (7.11)
|p(x)| |p(x)|

This completes our study of the wavefunction in the regions in which the
semi-classical approach can be formally justified. However, to make use of
this approximation, we have to understand how to deal with the regions close
to the classical turning points. Remember in our treatment of the Schrödinger
equation, energy quantization derived from the implementation of boundary
conditions.

7.4.3 Connection formulae, boundary conditions and quanti-

zation rules
Let us assume that we are dealing with a one-dimensional confining potential
where the classically allowed region is unique and spans the interval b ≤ x ≤ a.
Clearly, in the classically forbidden region to the right, x > a, only the first
term in Eq. (7.11) remains convergent and can contribute while, for x < b it
is only the second term that contributes. Moreover, in the classically allowed
region, b ≤ x ≤ a, the wavefunction has the oscillating form (7.10).
But how do we connect the three regions together? To answer this question,
it is necessary to make the assumption that the potential varies sufficiently
smoothly that it is a good approximation to take it to be linear in the vicinity of
the classical turning points. That is to say, we assume that a linear potential is
a sufficiently good approximation out to the point where the short wavelength
(or decay length for tunneling regions) description is adequate. Therefore,
near the classical turning at x = a, we take the potential to be

E − V (x) ( F0 (x − a) ,

where F0 denotes the (constant) force. For a strictly linear potential, the
wavefunction can be determined analytically, and takes the form of an Airy
function.7 In particular, it is known that the Airy function to the right of the
classical turning point has the asymptotic form
C Rx
lim ψ(x) = ' e−(1/!) a |p| dx ,
x&a 2 |p(x)|
7
For a detailed discussion in the present context, we refer to the text by Landau and
Lifshitz.

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 76

translating to a decay into the classically forbidden region while, to the left,
it has the asymptotic oscillatory solution,
6 $ a 7 6 $ 7
C 1 π C π 1 a
lim ψ(x) = ' cos p dx − ≡' cos − p dx .
b'x<a |p(x)| ! x 4 |p(x)| 4 ! x
At the second classical turning point at x = b, the same argument gives
6 $ x 7
C% 1 π
lim ψ(x) = ' cos p dx − .
b<x'a |p(x)| ! b 4
For these two expressions to be consistent, we must have C % = ±C and
" $ x # " $ #
1 π π 1 a
p dx − − − p dx = nπ ,
! b 4 4 ! x
where, for n% even, C % = C and for n odd, C % = −C. Therefore, we have the
a
condition !1 b p dx = (n + 1/2)π, or when cast in terms of a complete periodic
cycle of the classical motion,
8
p dx = 2π!(n + 1/2) .

This is just the Bohr-Sommerfeld quantization condition, and n can be

interpreted as the number of nodes of the wavefunction.
9
! Info. Note that the integrated action, p dx, represents the area of the clas-
sical path in phase space. This shows that each state is associated with an element
of phase space 2π!. From this, we can deduce the approximate energy splitting be-
tween levels in the semi-classical limit: The change in the integral with energy ∆E
corresponding to one level must be 2π! – one more state and one more node, i.e.
9 9 9
∆E ∂E p dx = 2π!. Now ∂p E = v, so ∂E p dx = dx/v = T , the period of the
orbit. Therefore, ∆E = 2π!/T = !ω: In the semi-classical limit, if a particle emits
one photon and drops to the next level, the frequency of the photon emitted is just
the orbital frequency of the particle.

p2
! Example: For the quantum harmonic oscillator, H = 2m + 12 mω 2 x2 = E,
the classical momentum is given by
: " #
mω 2 x2
p(x) = 2m E − .
2

The classical turning points are set by E = mω 2 x20 /2, i.e. x0 = ±2E/mω 2 . Over a
periodic cycle, the classical action is given by The WKB wavefunction (solid)
8 $ x0 : " # and the exact wavefunction
mω 2 x2 E (dashed) for the n = 0 and
p(x)dx = 2 dx 2m E − = 2π .
−x0 2 ω n = 10 states of the quantum
harmonic oscillator.
According to the WKB method, the latter must be equated to 2π!(n + 1/2), with
the last term reflecting the two turning points. As a result, we find that the energy
levels are as expected specified by En = (n + 1/2)!ω.
In the WKB approximation, the corresponding wavefunctions are given by
" $ x #
C 1 π
ψ(x) = ' cos p(x)dx −
p(x) ! −x0 4
" $ x #
C 2π 1 π
=' cos (n + 1/2) + p(x)dx −
p(x) 4 ! 0 4
3 - " # : .4
C nπ E x x x2
=' cos + arcsin + 1− 2 ,
p(x) 2 !ω x0 x0 x0

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7.4. WENTZEL, KRAMERS AND BRILLOUIN (WKB) METHOD 77

for 0 < x < x0 and

3 - : " #.4
C E x x2 x
ψ(x) = ' exp − 2 − 1 − arccosh x .
2 p(x) !ω x0 x0 0

for x > a. Note that the failure of the WKB approximation is reflected in the
appearance of discontinuities in the wavefunction at the classical turning points (see
figures). Nevertheless, the wavefunction at high energies provide a strikingly good
approximation to the exact wavefunctions.

! Example: As a second example, let us consider the problem of quantum

tunneling. Suppose that a beam of particles is incident upon a localized potential
barrier, V (x). Further, let us assume that, over a single continuous region of space,
from b to a, the potential rises above the incident energy of the incoming particles
so that, classically, all particles would be reflected. In the quantum system, the
some particles incident from the left may tunnel through the barrier and continue
propagating to the right. We are interested in finding the transmission probability.
From the WKB solution, to the left of the barrier (region 1), we expect a wave-
function of the form
6 $ x 7 6 $ 7
1 i 1 i x
ψ1 (x) = √ exp p dx + r(E) √ exp − p dx ,
p ! b p ! b
'
with p(E) = 2m(E − V (x)), while, to the right of the barrier (region 3), the wave-
function is given by
6 $ x 7
1 i
ψ3 (x) = t(E) √ exp p dx .
p ! a

In the barrier region, the wavefunction is given by

6 $ 7 6 $ x 7
C1 1 x C2 1
ψ2 (x) = ' exp − |p| dx + ' exp |p| dx .
|p(x)| ! a |p(x)| ! a

Then, applying the continuity condition on the wavefunction and its derivative at the
classical turning points, one obtains the transmissivity,
- $ .
2 b
T (E) ( exp − |p| dx .
! a

! Info. For a particle strictly confined to one dimension, the connection formulae
can be understood within a simple picture: The wavefunction “spills over” into the
classically forbidden region, and its twisting there collects an π/4 of phase change.
So, in the lowest state, the total phase change in the classically allowed region need
only be π/2. For the radial equation, assuming that the potential is well behaved
at the origin, the wavefunction goes to zero there. A bound state will still spill over
beyond the classical turning point at r0 , say, but clearly there must be a total phase
change of 3π/4 in the allowed region for the lowest state, since there can be no spill
over to negative r. In this case, the general quantization formula will be
$
1 r0
p(r) dr = (n + 3/4)π, n = 0, 1, 2, · · · ,
! 0
with the series terminating if and when the turning point reaches infinity. In fact,
some potentials, including the Coulomb potential and the centrifugal barrier for % '= 0,
are in fact singular at r = 0. These cases require special treatment.

Advanced Quantum Physics

Chapter 8

Identical Particles

Until now, most of our focus has been on the quantum mechanical behaviour
of individual particles, or problems which can be “factorized” into independent
single-particle systems.1 However, most physical systems of interest involve
the interaction of large numbers of particles; electrons in a solid, atoms in a gas,
etc. In classical mechanics, particles are always distinguishable in the sense
that, at least formally, their “trajectories” through phase space can be traced
and their identity disclosed. However, in quantum mechanics, the intrinsic
uncertainty in position, embodied in Heisenberg’s principle, demands a careful
and separate consideration of distinguishable and indistinguishable particles.
In the present section, we will consider how to formulate the wavefunction of
many-particle systems, and adress some of the (sometimes striking and often
counter-intuitive) implications of particle indistinguishability.

8.1 Quantum statistics

Consider then two identical particles confined to a box in one-dimension. Here,
by identical, we mean that the particles can not be discriminated by some
internal quantum number. For example, we might have two electrons of the
same spin. The normalized two-particle wavefunction ψ(x1 , x2 ), which gives
the probability |ψ(x1 , x2 )|2 dx1 dx2 of finding simultaneously one particle in
the interval x1 to x1 + dx1 and another between x2 to x2 + dx2 , only makes
sense if |ψ(x1 , x2 )|2 = |ψ(x2 , x1 )|2 , since we can’t know which of the two
indistinguishable particles we are finding where. It follows from this that the
wavefunction can exhibit two (and, generically, only two) possible symmetries
under exchange: ψ(x1 , x2 ) = ψ(x2 , x1 ) or ψ(x1 , x2 ) = −ψ(x2 , x1 ).2 If two
identical particles have a symmetric wavefunction in some state, particles of
that type always have symmetric wavefunctions, and are called bosons. (If
in some other state they had an antisymmetric wavefunction, then a linear
1
For example, our treatment of the hydrogen atom involved the separation of the system
into centre of mass and relative motion. Each could be referred to an effective single-particle
dynamics.
2
We could in principle have ψ(x1 , x2 ) = eiα ψ(x2 , x1 ), with α a constant phase. However,
in this case we would not recover the original wavefunction on exchanging the particles twice.
Curiously, in some two-dimensional theories used to describe the fractional quantum Hall
effect, there exist collective excitations of the electron system — called anyons — that do
have this kind of property. For a discussion of this point, one may refer to the seminal
paper of J. M. Leinaas and J. Myrheim, On the theory of identical particles. Il Nuovo
Cimento B37, 1-23 (1977). Such anyonic systems have been proposed as a strong candidate
for the realization of quantum computation. For a pedagogical discussion, we refer to an
entertaining discussion by C. Nayak, S. H. Simon, A. Stern, M. Freedman, S. Das Sarma,
Non-Abelian Anyons and Topological Quantum Computation, Rev. Mod. Phys. 80, 1083
(2008). However, all ordinary “fundamental” particles are either bosons or fermions.

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8.1. QUANTUM STATISTICS 79

superposition of those states would be neither symmetric nor antisymmetric,

and so could not satisfy the relation |ψ(x1 , x2 )|2 = |ψ(x2 , x1 )|2 .) Similarly,
particles having antisymmetric wavefunctions are called fermions.
To construct wavefunctions for three or more fermions, let first suppose
that the particles do not interact with each other, and are confined by a spin-
independent potential, such as the Coulomb field of a nucleus. In this case,
the Hamiltonian will be symmetric in the fermion degrees of freedom,

p̂21 p̂2 p̂2

Ĥ = + 2 + 3 · · · + V (r1 ) + V (r2 ) + V (r3 ) + · · · ,
2m 2m 2m
and the solutions of the Schrödinger equation will be products of eigenfunc-
tions of the single-particle Hamiltonian Ĥs = p̂2 /2m + V (r). However, sin-
gle products such as ψa (1)ψb (2)ψc (3) do not have the required antisymmetry
property under the exchange of any two particles. (Here a, b, c, ... label the
single-particle eigenstates of Ĥs , and 1, 2, 3,... denote both space and spin
coordinates of single particles, i.e. 1 stands for (r1 , s1 ), etc.)
We could achieve the necessary antisymmetrization for particles 1 and
2 by subtracting the same product wavefunction with the particles 1 and 2
interchanged, i.e. ψa (1)ψb (2)ψc (3) "→ (ψa (1)ψb (2)−ψa (2)ψb (1))ψc (3), ignoring
the overall normalization for now. However, the wavefunction needs to be
antisymmetrized with respect to all possible particle exchanges. So, for 3
particles, we must add together all 3! permutations of 1, 2, 3 in the state a, b,
c, with a factor −1 for each particle exchange necessary to get to a particular
ordering from the original ordering of 1 in a, 2 in b, and 3 in c. In fact, such a
sum over permutations is precisely the definition of the determinant. So, with
the appropriate normalization factor:
! !
! ψ (1) ψb (1) ψc (1) !
1 !! a !
ψabc (1, 2, 3) = √ ! ψa (2) ψb (2) ψc (2) !! .
3! ! ψ (3) ψ (3) ψ (3) !
a b c

The determinantal form makes clear the antisymmetry of the wavefunction

with respect to exchanging any two of the particles, since exchanging two
rows of a determinant multiplies it by −1. We also see from the determinantal
form that the three states a, b, c must all be different, for otherwise two
columns would be identical, and the determinant would be zero. This is just
the manifestation of Pauli’s exclusion principle: no two fermions can be in the
same state.
Although these determinantal wavefunctions (known as Slater determi-
nants), involving superpositions of single-particle states, are only strictly cor-
rect for non-interacting fermions, they provide a useful platform to describe
electrons in atoms (or in a metal), with the electron-electron repulsion ap-
proximated by a single-particle potential. For example, the Coulomb field in
an atom, as seen by the outer electrons, is partially shielded by the inner elec-
trons, and a suitable V (r) can be constructed self-consistently, by computing
the single-particle eigenstates and finding their associated charge densities (see
section 9.2.1).
In the bosonic system, the corresponding many-particle wavefunction must
be symmetric under particle exchange. We can obtain such a state by expand-
ing all of the contributing terms from the Slater determinant and setting all
of the signs to be positive. In other words, the bosonic wave function de-
scribes the uniform (equal phase) superposition of all possible permutations
of product states.

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8.2. SPACE AND SPIN WAVEFUNCTIONS 80

8.2 Space and spin wavefunctions

Although the metholodology for constructing a basis of many-particle states
outlined above is generic, it is not particularly convenient when the Hamil-
tonian is spin-independent. In this case we can simplify the structure of
the wavefunction by factorizing the spin and spatial components. Suppose
we have two electrons (i.e. fermions) in some spin-independent potential
V (r). We know that the two-electron wavefunction must be antisymmetric
under particle exchange. Since the Hamiltonian has no spin-dependence, we
must be able to construct a set of common eigenstates of the Hamiltonian,
the total spin, and the z-component of the total spin. For two electrons,
there are four basis states in the spin space, the S = 0 spin singlet state,
|χS=0,Sz =0 % = √12 (| ↑1 ↓2 % − | ↓1 ↑2 %), and the three S = 1 spin triplet states,

1
|χ11 % = | ↑1 ↑2 %, |χ10 % = √ (| ↑1 ↓2 % + | ↓1 ↑2 %) , |χ1,−1 % = | ↓1 ↓2 % .
2
Here the first arrow in the ket refers to the spin of particle 1, the second to
particle 2.

# Exercise. By way of revision, it is helpful to recapitulate the discussion of the Hint: begin by proving that, for
addition of spin s = 1/2 angular momenta. By setting S = S1 + S2 ,3 where S1 and S2 two spin s = 1/2 degree of free-
are two spin 1/2 degrees of freedom, construct the matrix elements of the total spin dom, S2 = S21 + S22 + 2S1 · S2 =
operator S2 for the four basis states, | ↑↑%, | ↑↓%, | ↓↑%, and | ↓↓%. From the matrix 2 × s(s + 1)!2 + 2S1z S2z + S1+ S2− +
S1− S2+ .
representation of S2 , determine the four eigenstates. Show that one corresponds to a
total spin zero state and three correspond to spin 1.

It is evident that the spin singlet wavefunction is antisymmetric under the

exchange of two particles, while the spin triplet wavefunction is symmetric.
For a general state, the total wavefunction for the two electrons in a common
eigenstate of S2 , Sz and the Hamiltonian Ĥ then has the form:

Ψ(r1 , s1 ; r2 , s2 ) = ψ(r1 , r2 )χ(s1 , s2 ) ,

where χ(s1 , s2 ) = )s1 , s2 |χ%. For two electron degrees of freedom, the to-
tal wavefunction, Ψ, must be antisymmetric under exchange. It follows that
a pair of electrons in the spin singlet state must have a symmetric spatial
wavefunction, ψ(r1 , r2 ), whereas electrons in the spin triplet states must have
an antisymmetric spatial wavefunction. Before discussing the physical conse-
quences of this symmetry, let us mention how this scheme generalizes to more
particles.

# Info. Symmetry of three-electron wavefunctions: Unfortunately, in

seeking a factorization of the Slater determinant into a product of spin and spatial
components for three electrons, things become more challenging. There are now
23 = 8 basis states in the spin space. Four of these are accounted for by the spin 3/2
state with Sz = 3/2, 1/2, −1/2, −3/2. Since all spins are aligned, this is evidently
a symmetric state, so must be multiplied by an antisymmetric spatial wavefunction,
itself a determinant. So far so good. But the other four states involve two pairs of
total spin 1/2 states built up of a singlet and an unpaired spin. They are orthogonal
to the symmetric spin 3/2 state, so they can’t be symmetric. But they can’t be
antisymmetric either, since in each such state, two of the spins must be pointing
in the same direction! An example of such a state is presented by |χ% = | ↑1 % ⊗
√1 (| ↑2 ↓3 % − | ↓2 ↑3 %). Evidently, this must be multiplied by a spatial wavefunction
2

3
Here, for simplicity, we have chosen not to include hats on the spin angular momentum
operators.

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8.3. PHYSICAL CONSEQUENCES OF PARTICLE STATISTICS 81

symmetric in 2 and 3. But to recover a total wave function with overall antisymmetry
it is necessary to add more terms:

Ψ(1, 2, 3) = χ(s1 , s2 , s3 )ψ(r1 , r2 , r3 ) + χ(s2 , s3 , s1 )ψ(r2 , r3 , r1 ) + χ(s3 , s1 , s2 )ψ(r3 , r1 , r2 ) .

Requiring the spatial wavefunction ψ(r1 , r2 , r3 ) to be symmetric in 2, 3 is sufficient

to guarantee the overall antisymmetry of the total wavefunction Ψ.4 For more than
three electrons, similar considerations hold. The mixed symmetries of the spatial
wavefunctions and the spin wavefunctions which together make a totally antisym-
metric wavefunction are quite complex, and are described by Young diagrams (or
tableaux).5 A discussion of this scheme reaches beyond the scope of these lectures.

# Exercise. A hydrogen atom consists of two fermions, the proton and the
electron. By considering the wavefunction of two non-interacting hydrogen atoms
under exchange, show that the atom transforms as a boson. In general, if the number
of fermions in a composite particle is odd, then it is a fermion, while if even it is
a boson. Quarks are fermions: baryons consist of three quarks and so translate to
fermions while mesons consist of two quarks and translate to bosons.

8.3 Physical consequences of particle statistics

The overall antisymmetry demanded by the many-fermion wavefunction has
important physical implications. In particular, it determines the magnetic
properties of atoms. The magnetic moment of the electron is aligned with its
spin, and even though the spin variables do not appear in the Hamiltonian,
the energy of the eigenstates depends on the relative spin orientation. This
arises from the electrostatic repulsion between electrons. In the spatially an-
tisymmetric state, the probability of electrons coinciding at the same position
necessarily vanishes. Moreover, the nodal structure demanded by the anti-
symmetry places the electrons further apart on average than in the spatially
symmetric state. Therefore, the electrostatic repulsion raises the energy of the
spatially symmetric state above that of the spatially antisymmetric state. It
therefore follows that the lower energy state has the electron spins pointing in
the same direction. This argument is still valid for more than two electrons,
and leads to Hund’s rule for the magnetization of incompletely filled inner
shells of electrons in transition metal and rare earths atoms (see chapter 9).
This is the first step in understanding ferromagnetism.
A gas of hydrogen molecules provides another manifestation of wavefunc-
tion antisymmetry. In particular, the specific heat depends sensitively on
whether the two protons (spin 1/2) in H2 have their spins parallel or antipar-
allel, even though that alignment involves only a very tiny interaction energy.
If the proton spins occupy a spin singlet configuration, the molecule is called
parahydrogen while the triplet states are called orthohydrogen. These two
distinct gases are remarkably stable - in the absence of magnetic impurities,
paraortho transitions take weeks.
The actual energy of interaction of the proton spins is of course completely
negligible in the specific heat. The important contributions to the specific heat
4
Particle physics enthusiasts might be interested to note that functions exactly like this
arise in constructing the spin/flavour wavefunction for the proton in the quark model (Grif-
fiths, Introduction to Elementary Particles, page 179).
5
For a simple introduction, see Sakurai’s textbook (section 6.5) or chapter 63 of the text
on quantum mechanics by Landau and Lifshitz.

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8.3. PHYSICAL CONSEQUENCES OF PARTICLE STATISTICS 82

are the usual kinetic energy term, and the rotational energy of the molecule.
This is where the overall (space × spin) antisymmetric wavefunction for the
protons plays a role. Recall that the parity of a state with rotational angular
momentum $ is (−1)! . Therefore, parahydrogen, with an antisymmetric pro-
ton spin wavefunction, must have a symmetric proton spatial wavefunction,
and so can only have even values of the rotational angular momentum. Or-
thohydrogen can only have odd values. The energy of the rotational level with
angular momentum $ is E!tot = !2 $($ + 1)/I, where I denotes the moment of
inertia of the molecule. So the two kinds of hydrogen gas have different sets
of rotational energy levels, and consequently different specific heats.

# Exercise. Determine the degeneracy of ortho- and parahydrogen. By ex-

pressing the state occupancy of the rotational states through the Boltzmann factor,
determine the low temperature variation of the specific heat for the two species.

# Example: As a final example, and one that will feed into our discussion of
multielectron atoms in the next chapter, let us consider the implications of particle
statistics for the excited state spectrum of Helium. After Hydrogen, Helium is
the simplest atom having two protons and two neutrons in the nucleus (Z = 2), and
two bound electrons. As a complex many-body system, we have seen already that the
Schrödinger equation is analytically intractable and must be treated perturbatively.
Previously, in chapter 7, we have used the ground state properties of Helium as a
vehicle to practice perturbation theory. In the absence of direct electron-electron
interaction, the Hamiltonian
2 # 2
" $
p̂ 1 Ze2
Ĥ0 = n
+ V (rn ) , V (r) = − ,
n=1
2m 4π&0 r

is separable and the wavefunction can be expressed through the states of the hydrogen
atom, ψn!m . In this approximation, the ground state wavefunction involves both
electrons occupying the 1s state leading to an antisymmetric spin singlet wavefunction
for the spin degrees of freedom, |Ψg.s. % = (|100% ⊗ |100%) ⊗ |χ00 %. In chapter 7, we
made use of both the perturbative series expansion and the variational method to
determine how the ground state energy is perturbed by the repulsive electron-electron
interaction,

1 e2
Ĥ1 = .
4π&0 |r1 − r2 |

Now let us consider the implications of particle statistics on the spectrum of the lowest
excited states.
From the symmetry perspective, the ground state wavefunction belongs to the
class of states with symmetric spatial wavefunctions, and antisymmetric spin (singlet)
wavefunctions. These states are known as parahelium. In the absence of electron-
electron interaction, the first excited states are degenerate and have the form,
1
|ψp % = √ (|100% ⊗ |2$m% + |2$m% ⊗ |100%) ⊗ |χ00 % .
2
The second class of states involve an antisymmetric spatial wavefunction, and sym-
metric (triplet) spin wavefunction. These states are known as orthohelium. Once
again, in the absence of electron-electron interaction, the first excited states are de-
generate and have the form,
1
|ψo % = √ (|100% ⊗ |2$m% − |2$m% ⊗ |100%) ⊗ |χ1Sz % .
2
The perturbative shift in the ground state energy has already been calculated
within the framework of first order perturbation theory. Let us now consider the shift

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8.4. IDEAL QUANTUM GASES 83

in the excited states. Despite the degeneracy, since the off-diagonal matrix elements
vanish, we can make use of the first order of perturbation theory to compute the shift.
In doing so, we obtain
%
p,o 1 e2 1
∆En! = d3 r1 d3 r2 |ψ100 (r1 )ψn!0 (r2 ) ± ψn!0 (r1 )ψ100 (r2 )|2 ,
2 4π&0 |r1 − r2 |
with the plus sign refers to parahelium and the minus to orthohelium. Since the
matrix element is independent of m, the m = 0 value considered here applies to all
p,o
values of m. Rearranging this equation, we thus obtain ∆En! = Jn! ± Kn! where
%
e2
|ψ100 (r1 )| |ψn!0 (r2 )|
2 2
Jn! = d 3 r1 d 3 r 2
4π&0 |r1 − r2 |
2 %
e ψ (r1 )ψn!0
∗ ∗
(r2 )ψ100 (r2 )ψn!0 (r1 )
Kn! = d3 r1 d3 r2 100 .
4π&0 |r1 − r2 |
Physically, the term Jn! represents the electrostatic interaction energy associated
with the two charge distributions |ψ100 (r1 )|2 and |ψn!0 (r2 )|2 , and it is clearly posi-
tive. By contrast, the exchange term, which derives from the antisymmetry of the
wavefunction, leads to a shift with opposite signs for ortho and para states. In fact,
one may show that, in the present case, Kn! is positive leading to a positive energy
shift for parahelium and a negative shift for orthohelium. Moreover, noting that
& ' (
3 1/2 triplet
2S1 · S2 = (S1 + S2 ) − S1 − S2 = ! S(S + 1) − 2 ×
2 2 2 2
=! 2
4 −3/2 singlet
the energy shift can be written as
& '
p,o 1 4
∆En! = Jn! − 1 + 2 S1 · S2 Kn! .
2 !
This result shows that the electron-electron interaction leads to an effective ferro-
magnetic interaction between spins – i.e. the spins want to be aligned.6
In addition to the large energy shift between the singlet and triplet states, electric Energy level diagram for ortho-
dipole decay selection rules ∆$ = ±1, ∆s = 0 (whose origin is discussed later in the and parahelium showing the first
course) cause decays from triplet to singlet states (or vice-versa) to be suppressed by order shift in energies due to
the Coulomb repulsion of elec-
a large factor (compared to decays from singlet to singlet or from triplet to triplet).
trons. Here we assume that one
This caused early researchers to think that there were two separate kinds of Helium. of the electrons stays close to the
The diagrams (right) shows the levels for parahelium (singlet) and for orthohelium ground state of the unperturbed
(triplet) along with the dominant decay modes. Hamiltonian.

8.4 Ideal quantum gases

An important and recurring example of a many-body system is provided by
the problem of free (i.e. non-interacting) non-relativistic quantum particles in
a closed system – a box. The many-body Hamiltonian is then given simply by
N
" p̂2i
Ĥ0 = ,
2m
i=1
where p̂i = −i!∇i and m denotes the particle mass. If we take the dimensions
of the box to be Ld , and the boundary conditions to be periodic7 (i.e. the box
6
A similar phenomenology extends to the interacting metallic system where the exchange
interaction leads to the phenomenon of itinerant (i.e. mobile) ferromagnetism – Stoner
ferromagnetism.
7
It may seem odd to consider such an unphysical geometry – in reality, we are invariably
dealing with a closed system in which the boundary conditions translate to “hard walls” –
think of electrons in a metallic sample. Here, we have taken the boundary conditions to be
periodic since it leads to a slightly more simple mathematical formulation. We could equally
well consider closed boundary conditions, but we would have to separately discriminate
between “even and odd” states and sum them accordingly. Ultimately, we would arrive to
the same qualitative conclusions!

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8.4. IDEAL QUANTUM GASES 84

Figure 8.1: (Left) Schematic showing the phase space volume associated with each
plane wave state in a Fermi gas. (Right) Schematic showing the state occupancy of a
filled Fermi sea.

has the geometry of a d-torus) the normalised eigenstates of the single-particle

Hamiltonian are simply given by plane waves, φk (r) = )r|k% = Ld/2 1
eik·r , with
wavevectors taking discrete values,8

2π
k= (n1 , n2 , · · · nd ), ni integer .
L
To address the quantum mechanics of the system, we start with fermions.

8.4.1 Non-interacting Fermi gas

In the (spinless) Fermi system, Pauli exclusion inhibits the multiple oc-
cupancy of single-particle states. In this case, the many-body ground state
wavefunction is obtained by filling states sequentially up to the Fermi en-
ergy, EF = !2 kF2 /2m, where the Fermi wavevector, kF , is fixed by the
number of particles. All the plane wave states φk with energies lower than
EF are filled, while all states with energies larger than EF remain empty.
Since each state is associated with a k-space volume (2π/L)d (see Fig. 8.1), in
the three-dimensional system, the total number of occupied states is given by
N = ( 2π ) 3 πkF3 , i.e. defining the particle density n = N/L3 = kF3 /6π 2 ,
L 34

!2 2
EF = (6π 2 n) 3 .
2m

The density of states per unit volume,

& '3/2 & '3/2
1 dN 1 d 2mE 1 2m
g(E) = 3 = 2 = 2 E 1/2 .
L dE 6π dE !2 4π !2
Note that the volume of a d-
dimensional sphere is given by
# Exercise. Obtain an expression for the density of states, g(E) in dimension 2π d/2
Sd = Γ(d/2) .
d. In particular, show that the density of states varies as g(E) ∼ E (d−2)/2 .

8
The quantization condition follows form the periodic boundary condition, φ[r+L(mx x̂+
my ŷ + mz ẑ)] = φ(r), where m = (mx , my , mz ) denotes an arbitrary vector of integers.

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8.4. IDEAL QUANTUM GASES 85

We can also integrate to obtain the total energy density of all the fermions,
%
Etot 1 kF
4πk 2 dk !2 k 2 !2 3
= 3 = (6π 2 n)5/3 = nEF .
L 3 L 0 (2π/L) 2m
3 20π m
2 5

# Info. Degeneracy pressure: The pressure exerted by fermions squeezed

into a small box is what keeps cold stars from collapsing. A White dwarf is a
remnant of a normal star which has exhausted its fuel fusing light elements into
heavier ones (mostly 56 Fe). As the star cools, it shrinks in size until it is arrested by
the degeneracy pressure of the electrons. If the white dwarf acquires more mass, the
Fermi energy EF rises until electrons and protons abruptly combine to form neutrons
and neutrinos, an event known as a supernova. The neutron star left behind is
supported by degeneracy pressure of the neutrons.
We can compute the degeneracy pressure from analyzing the dependence of the
energy on volume for a fixed number of particles (fermions). From thermodynamics,
we have dE = F · ds = P dV , i.e. the pressure P = −∂V Etot . The expression
for Etot given above shows that the pressure depends on the volume and particle
number N only through the density, n. To determine the point of collapse of stars,
we must compare this to the pressure exerted by gravity. We can compute this
approximately, ignoring general relativity and, more significantly, the variation of
gravitational pressure with radius. The mass contained within a shell of width dr
at radius r is given by dm = 4πρr2 dr, where ρ denotes the density. This mass
experiences a gravitational force from the mass contained within the shell, M =
3 πr ρ. The resulting potential energy is given by
4 3

% % The image shows the crab pul-

GM dm R
G( 43 πr3 ρ)4πr2 ρ (4π)2 2 5 3GM 2
EG = − =− d3 r =− Gρ R = − ,. sar, a magnetized neutron star
r r 15 5R
0
spinning at 30 times per second,
The mass of the star is dominated by nucleons, M = N MN , where MN denotes the that resides at the centre of the
nucleon mass and N their number. Substituting this expression into the formula for crab nebula. The pulsar pow-
4π 13
the energy, we find EG = − 35 G(N MN )2 ( 3V ) , from which we obtain the pressure, ers the X-ray and optical emis-
sion from the nebula, accelerat-
& '1/3 ing charged particles and pro-
1 4π
PG = −∂V EG = − G(N MN )2 V −4/3 . ducing the glowing X-ray jets.
5 3
Ring-like structures are X-ray
For the point of instability, this pressure must perfectly balance with the degener- emitting regions where the high
acy pressure. For a white dwarf, the degeneracy pressure is associated with electrons energy particles slam into the
and given by, nebular material. The innermost
ring is about a light-year across.
!2 With more mass than the Sun
Pe = −∂V Etot = (6π 2 Ne )5/3 V −5/3 .
60π 2 me and the density of an atomic nu-
cleus; the spinning pulsar is the
Comparing PG and Pe , we can infer the critical radius,
collapsed core of a massive star
5/3 that exploded, while the nebula
!2 N e
R≈ 2 N2 .
is the expanding remnant of the
Gme MN star’s outer layers. The super-
!2 1 nova explosion was witnessed in
Since there are about two nucleons per electron, NN ≈ 2Ne , R . Gme MN2 N−3 , the year 1054. The lower image
showing that radius decreases as we add mass. For one solar mass, N = 10 , we get 57
shows the typical size of a neu-
a radius of ca. 7200 km, the size of the Earth while EF . 0.2 MeV. tron star against Manhattan!
During the cooling period, a white dwarf star will shrink in size approaching the
critical radius. Since the pressure from electron degeneracy grows faster than the
pressure of gravity, the star will stay at about Earth size even when it cools. If the
star is more massive, the Fermi energy goes up and it becomes possible to absorb
the electrons into the nucleons, converting protons into neutrons. If the electrons
disappear this way, the star collapses suddenly down to a size for which the Fermi
pressure of the neutrons stops the collapse. Some white dwarfs stay at Earth size for a
long time as they suck in mass from their surroundings. When they have just enough
mass, they collapse forming a neutron star and making a supernova. The supernovae
are all nearly identical since the dwarfs are gaining mass very slowly. The brightness

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8.4. IDEAL QUANTUM GASES 86

of this type of supernova has been used to measure the accelerating expansion of the
universe. An estimate the neutron star radius using the formulae above leads to
Rneutron me
. . 10−3 ,
Rwhite dwarf MN
i.e. ca. 10 km. If the pressure at the center of a neutron star becomes too great, it Satyendra Nath Bose 1894-1974
collapses to become a black hole. An Indian physi-
cist who is best
known for his
work on quantum
mechanics in
8.4.2 Ideal Bose gas the early 1920s,
providing the
In a system of N spinless non-interacting bosons, the ground state of foundation for
the many-body system is described simply by a wavefunction in which all Bose-Einstein
statistics and the development of
N particles occupy the lowest energy single-particle state, i.e. in this case, the theory of the Bose-Einstein
the fully symmetrized ) wavefunction can be expressed as the product state, condensate. He is honored as the
ψB (r1 , r2 , · · · rN ) = N
i=1 φk=0 (ri ). (More generally, for a confining potential
namesake of the boson.

V (r), φk (r) denote the corresponding single-particle bound states with k the
associated quantum numbers.) However, in contrast to the Fermi system, the
transit to the ground state from non-zero temperatures has an interesting fea-
ture with intriguing experimental ramifications. To understand why, let us
address the thermodynamics of the system.
For independent bosons, the number of particles in plane wave state k with
energy &k is given by the Bose-Einstein distribution,

1
nk = ,
e(#k −µ)/kB T − 1
*
where the chemical potential, µ, is fixed by the condition N = k nk with
N the total number of particles. In a three-dimensional system, for N large,
we
* may Lapproximate
+ the sum by an integral over momentum space setting
k →
" ( 2π )3 d3 k. As a result, we find that

%
N 1 1
= n = d3 k (# −µ)/k T .
L3 (2π)3 e k B −1
!2 k2
For a free particle system, where &k = 2m , this means that

1
n= Li3/2 (µ/kB T ) , (8.1)
λ3T
* zk h2
where Lin (z) = ∞ k=1 kn denotes the polylogarithm, and λT = ( 2πmkB T )
1/2

denotes the thermal wavelength, i.e. the length scale at which the corre-
sponding energy scale becomes comparable to temperature. As the density of
particles increase, or the temperature falls, µ increases from negative values
until, at some critical value of density, nc = λ−3
T ζ(3/2), µ becomes zero (note
that Lin (0) = ζ(n)). Equivalently, inverting, this occurs at a temperature,

!2 2/3 2π
kB Tc = α n , α= .
m ζ 2/3 (3/2)

Clearly, since nk ≥ 0, the Bose distribution only makes sense for µ negative.
So what happens at this point?
Consider first what happens at zero temperature. Since the particles are
bosons, the ground state consists of every particle sitting in the lowest energy

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8.4. IDEAL QUANTUM GASES 87

state (k = 0). But such a singular distribution was excluded by the replace-
ment of the sum by the integral. Suppose that, at T < Tc , we have a thermo-
dynamic fraction f (T ) of particles sitting in this state.9 Then the chemical
potential may stay equal to zero and Eq. (8.1) becomes n = λ13 ζ(3/2)+f (T )n,
T
where f (T ) denotes the fraction of particles in the ground state. But, since
n = λ13 ζ(3/2), we have
Tc

& '3 & '3/2

λTc T
f (T ) = 1 − =1− .
λT Tc

The unusual, highly quantum degenerate state emerging below Tc is known as

a Bose-Einstein condensate (BEC).10 Note that,
% ∞
x2
# Exercise. Ideal Bose gas in a harmonic trap: Show that, in an harmonic dx x = 2ζ(3) ∼ 2.404 .
0 e −1
trap, V (r) = 21 mω 2 r2 , the corresponding relation is given by f (T ) = N [1 − ( TBEC
T
)3 ],
with kB Tc = !ω(N/ζ(3)) . 1/3

# Info. Although solid state systems continue to provide the most “accessible”
arena in which to study the properties of quantum liquids and gases, in recent years, a
new platform has been realized through developments in atomic physics – in the field of
ultracold atom physics, dilute atomic vapours are maintained at temperatures close
to absolute zero, typically below some tenths of microkelvins, where their behaviour
are influenced by the effects of quantum degneracy. The method of cooling the gas
has a long history which it would be unwise to detail here. But in short, alkali atoms
can be cooled by a technique known as laser cooling. Laser beams, in addition to
carrying heat, also carry momentum. As a result, photons impart a pressure when
they collide with atoms. The acceleration of an atom due to photons can be some four
orders of magnitude larger than gravity. Consider then a geometry in which atoms
are placed inside two counterprogating laser beams. To slow down, an atom has to
absorb a photon coming towards it, and not from behind. This can be arranged by
use of the Doppler shift. By tuning the laser frequency a little bit towards the low-
frequency (“red”) side of a resonance, the laser beam opposing the atom is Doppler
shifted to a higher (more “blue”) frequency. Thus the atom is more likely to absorb
that photon. A photon coming from behind the atom is now a little bit redder, which
means the atom is less likely to absorb that photon. So in whichever direction the
atom is moving, the laser beam opposing the motion seems stronger to the atom, and Schematic of a Magneto-Optical
it slows the atom down. If you multiply this by three and have laser beams coming Trap (MOT). The invention of
from the north, south, east, west, up, and down, you get an “optical molasse”. If the MOT in 1987 at Bell Labs
you walk around in a pot full of molasses, whichever direction you go, the molasses and optical molasses was the ba-
somehow knows that is the direction to push against. It’s the same idea. sis for the 1997 Nobel Prize in
In the study of ultracold atomic gases, experimentalists are usually concerned Physics.
with addressing the properties of neutral alkali atoms. The number of atoms in a
typical experiment ranges from 104 to 107 . The atoms are conned in a trapping
potential of magnetic or optical origin, with peak densities at the centre of the trap
ranging from 1013 cm3 to 1015 cm3 . The development of quantum phenomena such as
Bose-Einstein condensation requires a phase-space density of order unity, or nλ3T ∼ 1
where λT denotes the thermal de Broglie wavelength. These densities correspond to
temperatures,
!2 n2/3
T ∼ ∼ 100nK to a few µK .
mkB
9
Here, by thermodynamic, we mean that the fraction scales in proportion to the density.
10
The Bose-Einstein condensate was first predicted by Satyendra Nath Bose and Albert
Einstein in 1924-25. Bose first sent a paper to Einstein on the quantum statistics of light
quanta (now called photons). Einstein was impressed, translated the paper himself from
English to German and submitted it for Bose to the Zeitschrift fr Physik which published it.
Einstein then extended Bose’s ideas to material particles (or matter) in two other papers.

Advanced Quantum Physics

8.4. IDEAL QUANTUM GASES 88

Figure 8.2: (Left) Observation of BEC by absorption imaging. The top row shows
shadow pictures, which are rendered in a 3d plot below. The “sharp peak” is the
BEC, characterized by its slow expansion observed after 6 ms time of flight. The total
number of atoms at the phase transition is about 7 × 105 , and the temperature at the
transition point is 2 µK. (Figure from Ketterle.) (right) Figure shows the shrinking of
the atom cloud in a magnetic as the temperature is reduced by evaporative cooling.
Comparison between bosonic 7 Li (left) and fermionic 6 Li (right) shows the distinctive
signature of quantum statistics. The fermionic cloud cannot shrink below a certain
size determined by the Pauli exclusion principle. This is the same phenomenon that
prevents white dwarf and neutron stars from shrinking into black holes. At the
highest temperature, the length of the clouds was about 0.5mm. (Figure from J. R.
Anglin and W. Ketterle, Bose-Einstein condensation of atomic gases, Nature 416,
211 (2002).)

,
At these temperatures the atoms move at speeds of ∼ kB T /m ∼ 1 cm s−1 , which
should be compared with around 500 ms1 for molecules at room temperature, and
∼ 106 ms−1 for electrons in a metal at zero temperature. Achieving the regime n3T ∼ 1,
through sufficient cooling, is the principle experimental advance that gave birth to
this new field of physics.
It should be noted that such low densities of atoms are in fact a necessity. We are
dealing with systems whose equilibrium state is a solid (that is, a lump of Sodium,
Rubidium, etc.). The rst stage in the formation of a solid would be the combination
of pairs of atoms into diatomic molecules, but this process is hardly possible without
the involvement of a third atom to carry away the excess energy. The rate per atom
of such three-body processes is 1029 − 10−30 cm6 s−1 , leading to a lifetime of several
seconds to several minutes. These relatively long timescales suggest that working
with equilibrium concepts may be a useful first approximation.
Since the alkali elements have odd atomic number Z, we readily see that alkali Bosons Fermions
atoms with odd mass number are bosons, and those with even mass number are 7
Li I=3/2 6
Li I=1
fermions. Thus bosonic and fermionic alkalis have half-integer and integer nuclear 23
Na I=3/2 23
K I=4
spin respectively. Alkali atoms have a single valence electron in an ns state, so have 87
Rb I=3/2
electronic spin J = S = 1/2. The experimental star players: are shown in the table
(right). The hyperfine coupling between electronic and nuclear spin splits the ground
state manifold into two multiplets with total spin F = I ± 1/2. The Zeeman splitting
of these multiplets by a magnetic field forms the basis of magnetic trapping.
So, based on our discussion above, what happens when a Bose or Fermi gas is
confined by an harmonic trapping potential, V (r) = 12 mω 2 r2 . At high temperatures,
Bose and Fermi gases behave classically and form a thermal (Gaussian) distribution,
2 2
P (r) . e−mω r /2kB T . As the system is cooled towards the point of quantum degen-
eracy, i.e. when the typical separation between particles, n−1/3 , becomes comparable
to the thermal wavelength, λT , quantum statistics begin to impact. In the Fermi
system, Pauli exclusion leads to the development of a Fermi surface and the cloud
size becomes arrested. By contrast, the Bose system can form a BEC, with atoms
condensing into the ground state of the harmonic potential. Both features are shown
in Figure 8.2.

Advanced Quantum Physics

Chapter 9

Atomic structure

Previously, we have seen that the quantum mechanics of atomic hydrogen, and
hydrogen-like atoms is characterized by a large degeneracy with eigenvalues
separating into multiplets of n2 -fold degeneracy, where n denotes the principle
quantum number. However, although the idealized Schrödinger Hamiltonian,
p̂2 1 Ze2
Ĥ0 = + V (r), V (r) = − , (9.1)
2m 4π"0 r
provides a useful platform from which develop our intuition, there are several
important effects which mean that the formulation is a little too naı̈ve. These
“corrections”, which derive from several sources, are important as they lead to
physical ramifications which extend beyond the realm of atomic physics. Here
we outline some of the effects which need to be taken into account even for
atomic hydrogen, before moving on to discuss the quantum physics of multi-
electron atoms. In broad terms, the effects to be considered can be grouped
into those caused by the internal properties of the nucleus, and those which
derive from relativistic corrections.
To orient our discussion, it will be helpful to summarize some of key aspects
of the solutions of the non-relativisitic Schrödinger equation, Ĥ0 ψ = Eψ on
which we will draw:

Hydrogen atom revisited:

$ As with any centrally symmetric potential, the solutions of the Schrödinger

equation take the form ψ!m (r) = R(r)Y!m (θ, φ), where the spherical har-
monic functions Y!m (θ, φ) depend only on spherical polar coordinates,
and R(r) represents the radial component of the wavefunction. Solving
the radial wave equation introduces a radial quantum number, nr ≥ 0.
In the case of a Coulomb potential, the energy depends on the principal
quantum number n = nr + ' + 1 ≥ 1, and not on nr and ' separately.
$ For atomic hydrogen (Z = 1), the energy levels of the Hamiltonian (9.1)
are given by The fine structure constant is
! 2 " known to great accuracy and is
Ry e m e2 1 1 given by,
En = − 2 , Ry = = = mc2 α2 ,
n 4π"0 2! 2 4π"0 2a0 2
α = 7.297352570(5) × 10−3
4π#0 !2 e2 1
where a0 = is the Bohr radius, α = 4π#0 !cdenotes the fine 1
e2 m = .
structure constant, and strictly speaking m represents the reduced 137.035999070(9)
mass of the electron and proton. Applied to single electron ions with
higher atomic weight, such as He+ , Li2+ , etc., the Bohr radius is reduced
by a factor 1/Z, where Z denotes the nuclear charge, and the energy is
2
given by En = − Zn2 Ry = − 2n1 2 mc2 (Zα)2 .

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9.1. THE “REAL” HYDROGEN ATOM 90

$ Since n ≥ 1 and nr ≥ 0, the allowed combinations of quantum num-

bers are shown on the right, where we have introduced the conventional
notation whereby values of ' = 0, 1, 2, 3, 4 · · · are represented by letters n ' Subshell(s)
s, p, d, f, g · · · respectively. 1 0 1s
2 0, 1 2s 2p
$ Since En depends only on n, this implies, for example, an exact degen- 3 0, 1, 2 3s 3p 3d
eracy of the 2s and 2p, and of the 3s, 3p and 3d levels. 4 0, 1, 2, 3 4s 4p 4d 4f
n 0 · · · (n − 1) ns · · ·
These results emerge from a treatment of the hydrogen atom which is
inherently non-relativistic. In fact, as we will see later in our discussion of the
Dirac equation in chapter 15, the Hamiltonian (9.1) represents only the leading
term in an expansion in v 2 /c2 $ (Zα)2 of the full relativistic Hamiltonian To see that v 2 /c2 $ (Zα)2 , we
(see below). Higher order terms provide relativistic corrections, which impact may invoke the virial theorem.
significantly in atomic and condensed matter physics, and lead to a lifting of The latter shows that the aver-
the degeneracy. In the following we will discuss and obtain the heirarchy of age kinetic energy is related to
the potential energy as %T & =
leading relativistic corrections.1 This discussion will provide a platform to
− 12 %V &. Therefore, the aver-
describe multi-electron atoms. age energy is given by %E& =
%T & + %V & = −%T & ≡ − 21 mv 2 .
We therefore have that 12 mv 2 =
9.1 The “real” hydrogen atom Ry ≡ 21 mc2 (Zα)2 from which
follows the relation v 2 /c2 $
The relativistic corrections (sometimes known as the fine-structure cor- (Zα)2 .
rections) to the spectrum of hydrogen-like atoms derive from three different
sources:

$ relativistic corrections to the kinetic energy;

$ coupling between spin and orbital degrees of freedom;

$ and a contribution known as the Darwin term.

In the following, we will discuss each of these corrections in turn.

9.1.1 Relativistic correction to the kinetic energy

Previously, we have taken the kinetic energy to have the familiar non-relativistic
p̂2
form, 2m . However, from the expression for the relativistic energy-momentum
invariant, we can already anticipate that the leading correction to the non-
relativistic Hamiltonian appears at order p4 ,
# p2 1 (p2 )2
E = (pµ pµ )1/2 = p2 c2 + m2 c4 = mc2 + − + ···
2m 8 m3 c2
As a result, we can infer the following perturbation to the kinetic energy of
the electron,

1 (p̂2 )2
Ĥ1 = − .
8 m3 c2

When compared with the non-relativistic kinetic energy, p2 /2m, one can see
that the perturbation is smaller by a factor of p2 /m2 c2 = v 2 /c2 $ (Zα)2 , i.e.
Ĥ1 is only a small perturbation for small atomic number, Z ( 1/α $ 137.
1
It may seem odd to discuss relativistic corrections in advance of the Dirac equation
and the relativistic formulation of quantum mechanics. However, such a discussion would
present a lengthy and unnecessarily complex digression which would not lead to further
illumination. We will therefore follow the normal practice of discussing relativistic corrections
as perturbations to the familiar non-relativistic theory.

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9.1. THE “REAL” HYDROGEN ATOM 91

We can therefore make use of a perturbative analysis to estimate the scale of

the correction.
In principle, the large-scale degeneracy of the hydrogen atom would de-
mand an analysis based on the degenerate perturbation theory. However,
fortunately, since the off-diagonal matrix elements vanish,2

%n'm|Ĥ1 |n'! m! & = 0 for ' )= '! or m )= m! ,

degenerate states are uncoupled and such an approach is unnecessary. Then

making use of the identity, Ĥ1 = − 2mc
1
2 [Ĥ0 − V (r)] , the scale of the resulting
2

energy shift can be obtained from first order perturbation theory, By making use of the form of the
radial wavefunction for the hy-
1 & 2 '2 drogen atom, one may obtain the
%Ĥ1 &n!m ≡ %n'm|Ĥ1 |n'm& = − En − 2En %V (r)&n! + %V 2 (r)&n! .
2mc2 identities,
$ %
Since the calculation of the resulting expectation values is not particularly 1 Z
=
illuminating, we refer to the literature for a detailed exposition3 and present r n! a0 n2
here only the required identities (right). From these considerations, we obtain $ %
1 Z2
the following expression for the first order energy shift, = 2 3 .
2
r n! a0 n (' + 1/2)
! " ! "
mc2 Zα 4 n 3
%Ĥ1 &n!m = − − . (9.2)
2 n ' + 1/2 4

From this term alone, we expect the degerenacy between states with different
values of total angular momentum ' to be lifted. However, as well will see,
this conclusion is a little hasty. We need to gather all terms of the same
order of perturbation theory before we can reach a definite conclusion. We
can, however, confirm that (as expected) the scale of the correction is of order
"Ĥ1 #n!m
En ∼ ( Zα
n ) . We now turn to the second important class of corrections.
2

9.1.2 Spin-orbit coupling

As well as revealing the existence of an internal spin degree of freedom, the
relativistic formulation of quantum mechanics shows that there is a further
relativistic correction to the Schrödinger operator which involves a coupling
between the spin and orbital degrees of freedom. For a general potential V (r),
this spin-orbit coupling takes the form,

1 1
Ĥ2 = (∂r V (r)) Ŝ · L̂ .
2m2 c2 r
2
For a hydrogen-like atom, V (r) = − 4π#
1 Ze
0 r
, and

1 Ze2 1
Ĥ2 = Ŝ · L̂ .
2m2 c2 4π"0 r3

$ Info. Physically, the origin of the spin-orbit interaction can be understoon

from the following considerations. As the electron is moving through the electric
field of the nucleus then, in its rest frame, it will experience this as a magnetic
field. There will be an additional energy term in the Hamiltonian associated with
the orientation of the spin magnetic moment with respect to this field. We can make
an estimate of the spin-orbit interaction energy as follows: If we have a central field
determined by an electrostatic potential V (r), the corresponding electric field is given
2
The proof runs as follows: Since [Ĥ1 , L̂2 ] = 0, !2 [!! (!! + 1) − !(! + 1)] "n!m|Ĥ1 |n!! m! # =
0. Similarly, since [Ĥ1 , L̂z ] = 0, !(m! − m)"n!m|Ĥ1 |n!! m! # = 0.
3
see, e.g., Ref [1].

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9.1. THE “REAL” HYDROGEN ATOM 92

by E = −∇V (r) = −er (∂r V ). For an electron moving at velocity v, this translates
to an effective magnetic field B = c12 v × E. The magnetic moment of the electron
q
associated with its spin is equal to µs = gs 2m S ≡ −m
e
S, and thus the interaction
energy is given by
e e e 1
−µs · B = S · (v × E) = − S · (p × er (∂r V )) = (∂r V ) L · S ,
mc 2 (mc)2 (mc)2 r
where we have used the relation p × er = p × rr = − Lr . In fact this isn’t quite correct;
there is a relativistic effect connected with the precession of axes under rotation, called
Thomas precession which multiplies the formula by a further factor of 12 .

Once again, we can estimate the effect of spin-orbit coupling by treating Ĥ2
as a perturbation. In the absence of spin-orbit interaction, one may express
the eigenstates of hydrogen-like atoms in the basis states of the mutually
commuting operators, Ĥ0 , L̂2 , L̂z , Ŝ2 , and Ŝz . However, in the presence
of spin-orbit coupling, the total Hamiltonian no longer commutes with L̂z
or Ŝz (exercise). It is therefore helpful to make use of the degeneracy of
the unperturbed Hamiltonian to switch to a new basis in which the angular
momentum components of the perturbed system are diagonal. This can be
achieved by turning to the basis of eigenstates of the operators, Ĥ0 , Ĵ2 , Jˆz ,
L̂2 , and Ŝ2 , where Ĵ = L̂ + Ŝ denotes the total angular momentum. (For a
discussion of the form of these basis states, we refer back to section 6.4.2.)
Making use of the relation, Ĵ2 = L̂2 + Ŝ2 + 2L̂ · Ŝ, in this basis, it follows
that,
1
L̂ · Ŝ = (Ĵ2 − L̂2 − Ŝ2 ) .
2
Combining the spin and angular momentum, the total angular momentum
takes values j = ' ± 1/2. The corresponding basis states |j = ' ± 1/2, mj , '&
(with s = 1/2 implicit) therefore diagonalize the operator,
! "
!2 '
Ŝ · L̂|j = ' ± 1/2, mj , '& = |' ± 1/2, mj , '& ,
2 −' − 1
where the brackets index j = ' + 1/2 (top) and j = ' − 1/2 (bottom). As for
the radial dependence of the perturbation, once again, the off-diagonal matrix
elements vanish circumventing the need to invoke degenerate perturbation
theory. As a result, at first order in perturbation theory, one obtains
! " $ %
1 !2 ' Ze2 1
%H2 &n,j=!±1/2,mj ,! = .
2m c 2
2 2 −' − 1 4π"0 r3 n!
Then making use of the identity (right),4 one obtains For ' > 0,
! " ( ) $ % ! "3
1 2 Zα 4 n 1
1 mcαZ 1
%Ĥ2 &n,j=!±1/2,mj ,! = mc j
1 . = .
4 n j + 1/2 − j+1 r3 n! !n '(' + 12 )(' + 1)

Note that, for ' = 0, there is no orbital angular momentum with which to
couple! Then, if we rewrite the expression for %Ĥ1 & (9.2) in the new basis,
! " ( 1 )
1 2 Zα 4
%Ĥ1 &n,j=!±1/2,mj ,! = − mc n j
1 ,
2 n j+1

and combining both of these expressions, for ' > 0, we obtain

! " ! "
1 2 Zα 4 3 n
%Ĥ1 + Ĥ2 &n,j=!±1/2,mj ,! = mc − ,
2 n 4 j + 1/2
while for ' = 0, we retain just the kinetic energy term (9.2).
4
For details see, e.g., Ref [1].

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9.1. THE “REAL” HYDROGEN ATOM 93

9.1.3 Darwin term

The final contribution to the Hamiltonian from relativistic effects is known as
the Darwin term and arises from the “Zitterbewegung” of the electron –
trembling motion – which smears the effective potential felt by the electron.
Such effects lead to a perturbation of the form,
! "
!2 !2 e Ze2 !2
Ĥ3 = ∇ 2
V = Qnuclear (r) = 4πδ (3) (r) ,
8m c
2 2 8m c
2 2 "0 4π"0 8(mc)2

where Qnuclear (r) = Zeδ (3) (r) denotes the nuclear charge density. Since the
perturbation acts only at the origin, it effects only states with ' = 0. As a
result, one finds that
! "4
Ze2 !2 1 Zα
%Ĥ3 &njmj ! = 4π|ψ!n (0)|2 = mc2 nδ!,0 .
4π"0 8(mc)2 2 n

Intriguingly, this term is formally identical to that which would be obtained

from %Ĥ2 & at ' = 0. As a result, combining all three contributions, the total
energy shift is given simply by
! "4 ! "
1 Zα 3 n
∆En,j=!±1/2,mj ,! = mc2 − , (9.3)
2 n 4 j + 1/2

a result that is independent of ' and mj .

To discuss the predicted energy shifts for particular states, it is helpful to
introduce some nomenclature from atomic physics. For a state with principle
quantum number n, total spin s, orbital angular momentum ', and total an-
gular momentum j, one may use spectroscopic notation n2s+1 Lj to define
the state. For a hydrogen-like atom, with just a single electron, 2s + 1 = 2.
In this case, the factor 2s + 1 is often just dropped for brevity.
If we apply our perturbative expression for the relativistic corrections (9.3),
how do we expect the levels to shift for hydrogen-like atoms? As we have seen,
for the non-relativistic Hamiltonian, each state of given n exhibits a 2n2 -fold
degeneracy. For a given multiplet specified by n, the relativistic corrections
depend only on j and n. For n = 1, we have ' = 0 and j = 1/2: Both 1S1/2
states, with mj = 1/2 and −1/2, experience a negative energy shift by an
amount ∆E1,1/2,mj ,0 = − 41 Z 4 α2 Ry. For n = 2, ' can take the values of 0 or 1.
With j = 1/2, both the former 2S1/2 state, and the latter 2P1/2 states share
the same negative shift in energy, ∆E2,1/2,mj ,0 = ∆E2,1/2,mj ,1 = − 64 Z α Ry,
5 4 2

while the 2P3/2 experiences a shift of ∆E2,3/2,mj ,1 = − 64 Z α Ry. Finally, for

1 4 2

n = 3, ' can take values of 0, 1 or 2. Here, the pairs of states 3S1/2 and 3P1/2 ,
and 3P3/2 and 2D3/2 each remain degenerate while the state 3D5/2 is unique.
These predicted shifts are summarized in Figure 9.1.
This completes our discussion of the relativistic corrections which develop Willis Eugene Lamb, 1913-2008
from the treatment of the Dirac theory for the hydrogen atom. However, A physicist who
won the Nobel
this does not complete our discription of the “real” hydrogen atom. Indeed, Prize in Physics
there are further corrections which derive from quantum electrodynamics and in 1955 “for his
discoveries con-
nuclear effects which we now turn to address. cerning the fine
structure of the
hydrogen spectrum”. Lamb and
9.1.4 Lamb shift Polykarp Kusch were able to pre-
cisely determine certain electromag-
According to the perturbation theory above, the relativistic corrections which netic properties of the electron.
follow from the Dirac theory for hydrogen leave the 2S1/2 and 2P1/2 states
degenerate. However, in 1947, a careful experimental study by Willis Lamb

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9.1. THE “REAL” HYDROGEN ATOM 94

Figure 9.1: Figure showing the

heirarchy of energy shifts of the spec-
tra of hydrogen-like atoms as a result
of relativistic corrections. The first
column shows the energy spectrum
predicted by the (non-relativistic)
Bohr theory. The second column
shows the predicted energy shifts
from relativistic corrections arising
from the Dirac theory. The third col-
umn includes corrections due quan-
tum electrodynamics and the fourth
column includes terms for coupling
to the nuclear spin degrees of free-
dom. The H-α line, particularly
important in the astronomy, corre-
sponds to the transition between the
levels with n = 2 and n = 3.

and Robert Retherford discovered that this was not in fact the case:5 2P1/2 Hans Albrecht Bethe 1906-2005
A German-
state is slightly lower in energy than the 2S1/2 state resulting in a small shift American
of the corresponding spectral line – the Lamb shift. It might seem that such a physicist, and
tiny effect would be deemed insignificant, but in this case, the observed shift Nobel laureate
in physics “for
(which was explained by Hans Bethe in the same year) provided considerable his work on the
insight into quantum electrodynamics. theory of stellar
nucleosynthesis.”
In quantum electrodynamics, a quantized radiation field has a zero-point A versatile theo-
energy equivalent to the mean-square electric field so that even in a vacuum retical physicist,
Bethe also made important contribu-
there are fluctuations. These fluctuations cause an electron to execute an tions to quantum electrodynamics,
oscillatory motion and its charge is therefore smeared. If the electron is bound nuclear physics, solid-state physics
by a non-uniform electric field (as in hydrogen), it experiences a different and particle astrophysics. During
World War II, he was head of the
potential from that appropriate to its mean position. Hence the atomic levels Theoretical Division at the secret
are shifted. In hydrogen-like atoms, the smearing occurs over a length scale, Los Alamos laboratory developing
the first atomic bombs. There he
! "2 played a key role in calculating the
2α ! 1 critical mass of the weapons, and
%(δr)2 & $ ln , did theoretical work on the implosion
π mc αZ method used in both the Trinity test
and the “Fat Man” weapon dropped
some five orders of magnitude smaller than the Bohr radius. This causes the on Nagasaki.
electron spin g-factor to be slightly different from 2,
! "
α α2
gs = 2 1 + − 0.328 2 + · · · .
2π π

There is also a slight weakening of the force on the electron when it is very
close to the nucleus, causing the 2S1/2 electron (which has penetrated all the
way to the nucleus) to be slightly higher in energy than the 2P1/2 electron.
Taking into account these corrections, one obtains a positive energy shift
! "4 ! "
Z 8 1
∆ELamb $ nα Ry ×
2
α ln δ!,0 ,
n 3π αZ

for states with ' = 0.

5 Hydrogen fine structure and hy-
W. E. Lamb and R. C. Retherfod, Fine Structure of the Hydrogen Atom by a Microwave
Method, Phys. Rev. 72, 241 (1947).
perfine structure for the n = 3 to
n = 2 transition (see Fig. 9.1).

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9.1. THE “REAL” HYDROGEN ATOM 95

9.1.5 Hyperfine structure

So far, we have considered the nucleus as simply a massive point charge respon-
sible for the large electrostatic interaction with the charged electrons which
surround it. However, the nucleus has a spin angular momentum which is
associated with a further set of hyperfine corrections to the atomic spec-
tra of atoms. As with electrons, the protons and neutrons that make up a
nucleus are fermions, each with intrinsic spin 1/2. This means that a nucleus
will have some total nuclear spin which is labelled by the quantum number,
I. The latter leads to a nuclear magnetic moment,
Ze
µN = gN I.
2MN
where MN denotes the mass of the nucleus, and gN denotes the gyromagnetic
ratio. Since the nucleus has internal structure, the nuclear gyromagnetic ratio
is not simply 2 as it (nearly) is for the electron. For the proton, the sole
nuclear constituent of atomic hydrogen, gP ≈ 5.56. Even though the neutron
is charge neutral, its gyromagnetic ratio is about −3.83. (The consitituent
quarks have gyromagnetic ratios of 2 (plus corrections) like the electron but
the problem is complicated by the strong interactions which make it hard to
define a quark’s mass.) We can compute (to some accuracy) the gyromagnetic
ratio of nuclei from that of protons and neutrons as we can compute the
proton’s gyromagnetic ratio from its quark constituents. Since the nuclear
mass is several orders of magnitude higher than that of the electron, the nuclear
magnetic moment provides only a small perturbation.
According to classical electromagnetism, the magnetic moment generates
a magnetic field
µ0 2µ0
B= (3(µN · er )er − µN ) + µ δ (3) (r) .
4πr3 3 N
To explore the effect of this field, let us consider just the s-electrons, i.e. ' = 0,
for simplicity.6 In this case, the interaction of the magnetic moment of the
electrons with the field generated by the nucleus, gives rise to the hyperfine
interaction,
e
Ĥhyp = −µe · B = Ŝ · B .
mc
For the ' = 0 state, the first contribution to B vanishes while second leads to
the first order correction,
! "4
Z 8 m 1
%Hhyp &n,1/2,0 = nα2 Ry × gN S · I.
n 3 MN ! 2

Once again, to evaluate the expectation values on the spin degrees of free-
dom, it is convenient to define the total spin F = I + S. We then have
1 1 1
S · I = 2 (F2 − S2 − I2 ) = (F (F + 1) − 3/4 − I(I + 1))
! *2! 2
2

1 I F = I + 1/2
=
2 −I − 1 F = I − 1/2

Therefore, the 1s state of Hydrogen is split into two, corresponding to the

two possible values F = 0 and 1. The transition between these two levels has
frequency 1420 Hz, or wavelength 21 cm, so lies in the radio waveband. It
6
For a full discussion of the influence of the orbital angular momentum, we refer to Ref. [6].

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9.2. MULTI-ELECTRON ATOMS 96

is an important transition for radio astronomy. A further contribution to the

hyperfine structure arises if the nuclear shape is not spherical thus distorting
the Coulomb potential; this occurs for deuterium and for many other nuclei.
Finally, before leaving this section, we should note that the nucleus is not
point-like but has a small size. The effect of finite nuclear size can be A muon is a particle somewhat
estimated perturbatively. In doing so, one finds that the s (' = 0) levels are like an electron, but about 200
those most effected, because these have the largest probability of finding the times heavier. If a muon is
electron close to the nucleus; but the effect is still very small in hydrogen. It captured by an atom, the cor-
responding Bohr radius is 200
can be significant, however, in atoms of high nuclear charge Z, or for muonic
times smaller, thus enhancing
atoms. the nuclear size effect.

This completes our discussion of the “one-electron” theory. We now turn

to consider the properties of multi-electron atoms.

9.2 Multi-electron atoms

To address the electronic structure of a multi-electron atom, we might begin
with the hydrogenic energy levels for an atom of nuclear charge Z, and start
filling the lowest levels with electrons, accounting for the exclusion principle.
The degeneracy for quantum numbers (n, ') is 2 × (2' + 1), where (2' + 1) is
the number of available m! values, and the factor of 2 accounts for the spin
degeneracy. Hence, the number of electrons accommodated in shell, n, would
be 2 × n2 ,
n ' Degeneracy in shell Cumulative total
1 0 2 2
2 0, 1 (1 + 3) × 2 = 8 10
3 0, 1, 2 (1 + 3 + 5) × 2 = 18 28
4 0, 1, 2, 3 (1 + 3 + 5 + 7) × 2 = 32 60
We would therefore expect that atoms containing 2, 10, 28 or 60 electrons
would be especially stable, and that in atoms containing one more electron
than this, the outermost electron would be less tightly bound. In fact, if we
look at data (Fig. 9.2) recording the first ionization energy of atoms, i.e. the
minimum energy needed to remove one electron, we find that the noble gases,
having Z = 2, 10, 18, 36 · · · are especially tightly bound, and the elements
containing one more electron, the alkali metals, are significantly less tightly
bound.
The reason for the failure of this simple-minded approach is fairly obvious –
we have neglected the repulsion between electrons. In fact, the first ionization
energies of atoms show a relatively weak dependence on Z; this tells us that the
outermost electrons are almost completely shielded from the nuclear charge.7
Indeed, when we treated the Helium atom as an example of the variational
method in chapter 7, we found that the effect of electron-electron repulsion
was sizeable, and really too large to be treated accurately by perturbation
theory.
7
In fact, the shielding is not completely perfect. For a given energy shell, the effective
nuclear charge varies for an atomic number Z as Zeff ∼ (1 + α)Z where α > 0 characterizes
2
the ineffectiveness of screening. This implies that the ionization energy IZ = −EZ ∼ Zeff ∼
(1 + 2αZ). The near-linear dependence of IZ on Z is reflected in Fig. 9.2.

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9.2. MULTI-ELECTRON ATOMS 97

Figure 9.2: Ionization energies of the elements.

9.2.1 Central field approximation

Leaving aside for now the influence of spin or relativistic effects, the Hamilto-
nian for a multi-electron atom can be written as
+ , !2 1 Ze2
- +
1 e2
Ĥ = − 2
∇i − + ,
2m 4π"0 ri 4π"0 rij
i i<j

where rij ≡ |ri − rj |. The first term represents the “single-particle” contri-
bution to the Hamiltonian arising from interaction of each electron with the
nucleus, while the last term represents the mutual Coulomb interaction be-
tween the constituent electrons. It is this latter term that makes the generic
problem “many-body” in character and therefore very complicated. Yet, as we
have already seen in the perturbative analysis of the excited states of atomic
Helium, this term can have important physical consequences both on the over-
all energy of the problem and on the associated spin structure of the states.
The central field approximation is based upon the observation that
the electron interaction term contains a large central (spherically symmetric)
component arising from the “core electrons”. From the following relation,
!
+
|Ylm (θ, φ)|2 = const.
m=−!

it is apparent that a closed shell has an electron density distribution which

is isotropic (independent of θ and φ). We can therefore develop a perturbative
scheme by setting Ĥ = Ĥ0 + Ĥ1 , where
+ , !2 1 Ze2
- + 1 e2 +
Ĥ0 = − 2
∇i − + Ui (ri ) , Ĥ1 = − Ui (ri ) .
2m 4π"0 ri 4π"0 rij
i i<j i

Here the one-electron potential, Ui (r), which is assumed central (see below),
incorporates the “average” effect of the other electrons. Before discussing how
to choose the potentials Ui (r), let us note that Ĥ0 is separable into a sum of
terms for each electron, so that the total wavefunction can be factorized into
components for each electron. The basic idea is first to solve the Schrödinger
equation using Ĥ0 , and then to treat Ĥ1 as a small perturbation.
On general grounds, since the Hamiltonian Ĥ0 continues to commute with
the angular momentum operator, [Ĥ0 , L̂] = 0, we can see that the eigenfunc-
tions of Ĥ0 will be characterized by quantum numbers (n, ', m! , ms ). However,

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9.2. MULTI-ELECTRON ATOMS 98

since the effective potential is no longer Coulomb-like, the ' values for a given Douglas Rayner Hartree FRS
n need not be degenerate. Of course, the difficult part of this procedure is 1897-1958
An English
to estimate Ui (r); the potential energy experienced by each electron depends mathematician
on the wavefunction of all the other electrons, which is only known after the and physicist
most famous for
Schrödinger equation has been solved. This suggests that an iterative approach the development
to solving the problem will be required. of numerical
analysis and its
To understand how the potentials Ui (r) can be estimated – the self- application to
consistent field method – it is instructive to consider a variational ap- atomic physics.
proach due originally to Hartree. If electrons are considered independent, the He entered
St John’s College Cambridge in
wavefunction can be factorized into the product state, 1915 but World War I interrupted
his studies and he joined a team
Ψ({ri }) = ψi1 (r1 )ψi2 (r2 ) · · · ψiN (rN ) , studying anti-aircraft gunnery. He
returned to Cambridge after the war
where the quantum numbers, ik ≡ (n'm! ms )k , indicate the individual state and graduated in 1921 but, perhaps
because of his interrupted studies,
occupancies. Note that this product state is not a properly antisymmetrized he only obtained a second class
Slater determinant – the exclusion principle is taken into account only in so degree in Natural Sciences. In 1921,
a visit by Niels Bohr to Cambridge
far as the energy of the ground state is taken to be the lowest that is consistent inspired him to apply his knowledge
with the assignment of different quantum numbers, n'm! ms to each electron. of numerical analysis to the solution
of differential equations for the
Nevertheless, using this wavefunction as a trial state, the variational energy is calculation of atomic wavefunctions.
then given by
+. ! 2 2 "
∗ ! ∇ 1 Ze2
E = %Ψ|Ĥ|Ψ& = 3
d r ψi − − ψi
2m 4π"0 r
i
. .
1 + e2
+ 3
d r d3 r! ψi∗ (r)ψi∗ (r! ) ψj (r! )ψi (r) .
4π"0 |r − r! |
i<j

Now, according to the variational principle, we must minimize the energy

functional by varying E[{ψi }] with respect to the complex wavefunction, ψi ,
subject to the normalization condition, %ψi |ψi & = 1. The latter can be imposed
using a set of Lagrange multipliers, εi , i.e.
, !. "-
δ
E − εi d r|ψi (r)| − 1
3 2
= 0.
δψi∗
Following the variation,8 one obtains the Hartree equations,
! 2 2 " .
! ∇ 1 Ze2 1 + e2
− − ψi + d3 r! |ψj (r! )|2 ψi (r)
2m 4π"0 r 4π"0 |r − r! |
j&=i
= εi ψi (r) . (9.4)
Then according to the variational principle, amongst all possible trial functions
ψi , the set that minimizes the energy are determined by the effective potential,

.
1 + e2
Ui (r) = d3 r! |ψj (r! )|2 .
4π"0 |r − r! |
j&=i

Equation (9.4) has a simple interpretation: The first two terms relate to the
nuclear potential experienced by the individual electrons, while the third term
represents the electrostatic potential due to the other electrons. However, to
simplify the procedure, it is useful to engineer the radial symmetry of the
potential by replacing Ui (r) by its spherical average,
.
dΩ
Ui (r) -→ Ui (r) = Ui (r) .
4π
8
Note that, in applying the variation, the wavefunction ψi∗ can be considered independent
of ψi – you might like to think why.

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9.2. MULTI-ELECTRON ATOMS 99

Finally, to relate the Lagrange multipliers, εi (which have the appearance

of one-electron energies), to the total energy, we can multiply Eq. (9.4) by
ψi∗ (r) and integrate,
. ! 2 2 "
∗ ! ∇ 1 Ze2
"i = d r ψi −
3
− ψi
2m 4π"0 r
.
1 + e2
+ d3 r! d3 r |ψj (r! )|2 |ψi (r)|2 .
4π"0 |r − r! |
j&=i

If we compare this expression with the variational state energy, we find that
+ .
1 + e2
E= "i − d3 r! d3 r |ψj (r! )|2 |ψi (r)|2 . (9.5)
4π"0 |r − r! |
i i<j

To summarize, if we wish to implement the central field approximation to

determine the states of a multi-electron atom, we must follow the algorithm:

1. Firstly, one makes an initial “guess” for a (common) central potential,

U (r). As r → 0, screening becomes increasingly ineffective and we ex-
1 (Z−1)e2
pect U (r) → 0. As r → ∞, we anticipate that U (r) → 4π# 0 r ,
corresponding to perfect screening. So, as a starting point, we make
take some smooth function U (r) interpolating between these limits. For
this trial potential, we can solve (numerically) for the eigenstates of the
single-particle Hamiltonian. We can then use these states as a plat-
form to build the product wavefunction and in turn determine the self-
consistent potentials, Ui (r).

2. With these potentials, Ui (r), we can determine a new set of eigenstates

for the set of Schrödinger equations,
, -
!2 2 1 Ze2
− ∇ − + Ui (r) ψi = εi ψi .
2m 4π"0 r

3. An estimate for the ground state energy of an atom can be found by

filling up the energy levels, starting from the lowest, and taking account
of the exclusion principle.

4. Using these wavefunctions, one can then make an improved estimate of

the potentials Ui (ri ) and return to step 2 iterating until convergence.

Since the practical implemention of such an algorithm demands a large degree

of computational flair, if you remain curious, you may find it useful to refer to
the Mathematica code prepared by Ref. [4] where both the Hartree and the
Hartree-Fock procedures (described below) are illustrated.

$ Info. An improvement to this procedure, known the Hartree-Fock method,

takes account of exchange interactions. In order to do this, it is necessary to ensure
that the wavefunction, including spin, is antisymmetric under interchange of any pair
of electrons. This is achieved by introducing the Slater determinant. Writing the
individual electron wavefunction for the ith electron as ψk (ri ), where i = 1, 2 · · · N and
k is shorthand for the set of quantum numbers (n'm! ms ), the overall wavefunction
is given by
/ /
/ ψ1 (r1 ) ψ1 (r2 ) ψ1 (r3 ) · · · /
/ /
1 // ψ2 (r1 ) ψ2 (r2 ) ψ2 (r3 ) · · · //
Ψ = √ / ψ3 (r1 ) ψ3 (r2 ) ψ3 (r3 ) · · · / .
N ! // /
.. .. .. . . //
/ . . . .

Advanced Quantum Physics

9.2. MULTI-ELECTRON ATOMS 100

Note that each of√the N ! terms in Ψ is a product of wavefunctions for each individual Vladimir Aleksandrovich Fock
electron. The 1/ N ! factor ensures the wavefunction is normalized. A determinant 1898-1974
A Soviet physi-
changes sign if any two columns are exchanged, corresponding to ri ↔ rj (say); this cist, who did
ensures that the wavefunction is antisymmetric under exchange of electrons i and j. foundational
Likewise, a determinant is zero if any two rows are identical; hence all the ψk s must work on quan-
be different and the Pauli exclusion principle is satisfied.9 In this approximation, a tum mechanics
and quantum
variational analysis leads to the Hartree-Fock equations (exercise), electrodynamics.
, - His primary
!2 2 Ze2
εi ψi (r) = − ∇i − ψi (r) scientific con-
2m 4π"ri tribution lies
+. 1 e2 0 1 in the development of quantum
+ d 3 rj ψ (r
∗ #
) ψ j (r#
)ψ i (r) − ψ j (r)ψ i (r#
)δ m ,m . physics, although he also contributed
4π"0 |r − r# | j s i s j
significantly to the fields of me-
j"=i
chanics, theoretical optics, theory of
The first term in the last set of brackets translates to the ordinary Hartree contribution gravitation, physics of continuous
above and describes the influence of the charge density of the other electrons, while medium. In 1926 he derived the
Klein-Gordon equation. He gave
the second term describes the non-local exchange contribution, a manifestation of his name to Fock space, the Fock
particle statistics. representation and Fock state, and
developed the HartreeFock method
in 1930. Fock made significant
The outcome of such calculations is that the eigenfunctions are, as for contributions to general relativity
theory, specifically for the many
hydrogen, characterized by quantum numbers n, ', m! , with ' < n, but that the body problems.
states with different ' for a given n are not degenerate, with the lower values
of ' lying lower. This is because, for the higher ' values, the electrons tend
to lie further from the nucleus on average, and are therefore more effectively
screened. The states corresponding to a particular value of n are generally
referred to as a shell, and those belonging to a particular pair of values of n, '
are usually referred to as a subshell. The energy levels are ordered as below
(with the lowest lying on the left): !
"
Subshell name 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d ··· !
!
"
! !
7s 7p
! ! 7d
n= 1 2 2 3 3 4 3 4 5 4 ··· ···
!
"
!
'= 0 0 1 0 1 0 2 1 0 2 ··· 6s !
6p !
6d 6f · · ·
!
" ! ! !
Degeneracy 2 2 6 2 6 2 10 6 2 10 ··· ! 5p 5d
5s ! ! 5g
! 5f
Cumulative 2 4 10 12 18 20 30 36 38 48 ··· " ! ! ! !
!
4s 4p
! ! 4d
! 4f!
Note that the values of Z corresponding to the noble gases, 2, 10, 18, 36, at " ! ! ! !!
!
! 3p
3s ! 3d!
which the ionization energy is unusually high, now emerge naturally from this " ! ! !!
!
filling order, corresponding to the numbers of electrons just before a new shell 2s
! !2p
" ! !!
!
(n) is entered. There is a handy mnemonic to remember this filling order. By 1s
! !
writing the subshells down as shown right, the order of states can be read off !
along diagonals from lower right to upper left, starting at the bottom.
We can use this sequence of energy levels to predict the ground state
electron configuration of atoms. We simply fill up the levels starting from
the lowest, accounting for the exclusion principle, until the electrons are all
accommodated (the aufbau principle). Here are a few examples:
Z Element Configuration 2S+1
LJ Ioniz. Pot. (eV)
1 H (1s) 2
S1/2 13.6
2 He (1s)2 1
S0 24.6
3 Li He (2s) 2
S1/2 5.4
4 Be He (2s)2 1
S0 9.3
5 B He (2s)2 (2p) 2
P1/2 8.3
6 C He (2s)2 (2p)2 3
P0 11.3
7 N He (2s)2 (2p)3 4
S3/2 14.5
8 O He (2s)2 (2p)4 3
P2 13.6
9 F He (2s)2 (2p)5 2
P3/2 17.4
10 Ne He (2s)2 (2p)6 1
S0 21.6
11 Na Ne (3s) 2
S1/2 5.1
9
Note that for N = 2, the determinant reduces to the familiar antisymmetric wavefunc-
tion, √12 [ψ1 (r1 )ψ2 (r2 ) − ψ2 (r1 )ψ1 (r2 )].

Advanced Quantum Physics

9.2. MULTI-ELECTRON ATOMS 101

Figure 9.3: Periodic table of elements.

Since it is generally the outermost electrons which are of most interest, con-
tributing to chemical activity or optical spectra, one often omits the inner
closed shells, and just writes O as (2p)4 , for example. However, the configura-
tion is not always correctly predicted, especially in the heavier elements, where
levels may be close together. It may be favourable to promote one or even
two electrons one level above that expected in this simple picture, in order to
achieve a filled shell. For example, Cu (Z = 29) would be expected to have con-
figuration · · · (4s)2 (3d)9 , and actually has configuration · · · (4s)1 (3d)10 . There
are several similar examples in the transition elements where the d subshells
are being filled, and many among the lanthanides (rare earths) and actinides
where f subshells are being filled.

$ Info. Since the assignment of an electron configuration requires only the

enumeration of the values of n and ' for all electrons, but not those of m! and ms ,
each configuration will be accompanied by a degeneracy g. If νn! denotes the number
of electrons occupying a given level En,! , and δ! = 2 × (2' + 1) is the degeneracy of
that level, there are
δ! !
dn! = (9.6)
νn! !(δ! − νn! )!

ways of distributing the νn! electrons among the δ! individual states. The total
degeneracy, g, is then obtained from the product.

This scheme provides a basis to understand the periodic table of el-

ements (see Fig. 9.3). We would expect that elements which have similar
electron configurations in their outermost shells (such as Li, Na, K, Rb, Cs, Fr
which all have (ns)1 or F, Cl, Br, I, which all have (np)5 ) would have similar
chemical properties, such as valency, since it is the unpaired outer electrons
which especially participate in chemical bonding. Therefore, if one arranges
the atoms in order of increasing atomic number Z (which equals the number
of electrons in the atom), periodic behaviour is seen whenever a new subshell
of a given ' is filled.

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9.3. COUPLING SCHEMES 102

9.3 Coupling schemes

The procedure outlined above allows us to predict the occupation of subshells
in an atomic ground state. This is not in general sufficient to specify the ground
state fully. If there are several electrons in a partially filled subshell, then their
spins and orbital angular momenta can combine in several different ways, to
give different values of total angular momentum, with different energies. In
order to deal with this problem, it is necessary to consider the spin-orbit
interaction as well as the residual Coulomb interaction between the outer
electrons.
Schematically we can write the Hamiltonian for this system as follows:
+ 1 e2 + +
Ĥ ≈ Ĥ0 + − Ui (r) + ξi (ri )L̂i · Ŝi ,
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ 2

where Ĥ0 includes the kinetic energy and central field terms, Ĥ1 is the residual
Coulomb interaction, and (with ξi (ri ) = 2m12 c2 1r (∂r V (r))) Ĥ2 is the spin-orbit
interaction. We can then consider two possible scenarios:

Ĥ1 2 Ĥ2 : This tends to apply in the case of light atoms. In this situation,
one considers first the eigenstates of Ĥ0 + Ĥ1 , and then treats Ĥ2 as a
perturbation. This leads to a scheme called LS (or Russell-Saunders)
coupling.

Ĥ2 2 Ĥ1 : This can apply in very heavy atoms, or in heavily ionized light
atoms, in which the electrons are moving at higher velocities and rela-
tivistic effects such as the spin-orbit interaction are more important. In
this case, a scheme called jj coupling applies.

It is important to emphasise that both of these scenarios represent approxima-

tions; real atoms do not always conform to the comparatively simple picture
which emerges from these schemes, which we now discuss in detail.

9.3.1 LS coupling scheme

In this approximation, we start by considering the eigenstates of Ĥ0 + Ĥ1 . We
note that this Hamiltonian must commute with the total angular momentum
Ĵ2 (because of invariance under rotations in space), and also clearly commutes
with the total spin Ŝ2 . It also commutes with the total orbital angular momen-
tum L̂2 , since Ĥ1 only involves internal interactions, and must therefore be
invariant under global rotation of all the electrons. Therefore the energy levels
can be characterised by the corresponding total angular momentum quantum
numbers L, S, J. Their ordering in energy is given by Hund’s rules:

1. Combine the spins of the electrons to obtain possible values of total spin
S. The largest permitted value of S lies lowest in energy.

2. For each value of S, find the possible values of total angular momentum
L. The largest value of L lies lowest in energy.

3. Couple the values of L and S to obtain the values of J (hence the name
of the scheme). If the subshell is less than half full, the smallest value
of J lies lowest; otherwise, the largest value of J lies lowest.

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9.3. COUPLING SCHEMES 103

In deciding on the permitted values of L and S, in addition to applying the

usual rules for adding angular momenta, one also has to ensure that the exclu-
sion principle is respected, as we will see later when considering some examples.
These rules are empirical; there are exceptions, especially to the L and J
rules (2 and 3). Nevertheless, Hund’s rules are a useful guide, and we should
try to understand their physical origin.

1. Maximising S makes the spin wavefunction as symmetric as possible.

This tends to make the spatial wavefunction antisymmetric, and hence
reduces the Coulomb repulsion, as we saw when discussing the exchange
interactions in Helium.

2. Maximising L also tends to keep the electrons apart. This is less obvious,
though a simple classical picture of electrons rotating round the nucleus
in the same or different senses makes it at least plausible.

3. The separation of energies for states of different J arises from treating

the spin-orbit term Ĥ2 as a perturbation (fine structure). It can be
shown (using the Wigner-Eckart theorem – beyond the scope of these
lectures) that
+
%|J, mJ , L, S| ξi (ri )L̂i · Ŝi |J, mJ , L, S&
i
= ζ(L, S)%J, mJ , L, S|L̂ · Ŝ|J, mJ , L, S&
ζ(L, S)
= [J(J + 1) − L(L + 1) − S(S + 1)] , (9.7)
2
where the matrix element ζ(L, S) depends on the total L and S values.
Since one may show that the sign of ζ(L, S) changes according to the
whether the subshell is more or less than half-filled, the third Hund’s
rule is established.

To understand the application of LS coupling, it is best to work through

some examples. Starting with the simplest multi-electron atom, helium, the
ground state has an electron configuration (1s)2 , and must therefore have
L = S = J = 0. In fact, for any completely filled subshell, we have L = S = 0
and hence J = 0, since the total mL and mS must equal zero if all substates
are occupied. Consider now an excited state of helium, e.g. (1s)1 (2p)1 , in
which one electron has been excited to the 2p level. We can now have S = 1
or S = 0, with the S = 1 state lying lower in energy according to Hund’s
rules. Combining the orbital angular momenta of the electrons yields L = 1
and thus, with S = 0, J = 1, while with S = 1, J = 0, 1, 2 with J = 0 lying
lowest in energy.
Once again, as with the hydrogen-like states, we may index the states of
multi-electron atoms by spectroscopic term notation, 2S+1 LJ . The superscript
2S + 1 gives the multiplicity of J values into which the level is split by the
spin-orbit interaction; the L value is represented by a capital letter, S, P , D,
etc., and J is represented by its numerical value. Thus, for the (1s)1 (2p)1
state of helium, there are four possible states, with terms:
3
P0 3 P1 3 P2 1
P1 ,

where the three 3 P states are separated by the spin-orbit interaction, and the
singlet 1 P state lies much higher in energy owing to the Coulomb interaction.
The separations between the 3 P2 and 3 P1 and the 3 P1 and 3 P0 should be in the

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9.3. COUPLING SCHEMES 104

ratio 2:1. This is an example of the Landé interval rule, which states that
the separation between a pair of adjacent levels in a fine structure multiplet is
proportional to the larger of the two J values involved. This is easily shown
using Eq. (9.7) – the separation in energy between states J and J − 1 is

∝ J(J + 1) − (J − 1)J = 2J .

Actually in the case of helium the situation is a bit more complicated, because
it turns out that the spin-orbit interaction between different electrons makes
a non-negligible additional contribution to the fine structure. Other excited
states of helium, of the form (1s)1 (n')1 , can be handled similarly, and again
separate into singlet and triplet states.

$ Exercise. For the case of boron, with the electron configuration (1s)2 (2s)2 (2p),
use Hund’s rules to show that the ground state is 2 P1/2 .

We next consider the case of carbon, which has ground state electron
configuration (1s)2 (2s)2 (2p)2 . This introduces a further complication; we now
have two identical electrons in the same unfilled subshell, and we need to
ensure that their wavefunction is antisymmetric with respect to electron ex-
change. The total spin can either be the singlet S = 0 state, which has an
antisymmetric wavefunction √12 [| ↑1 & ⊗ | ↓2 & − | ↓1 & ⊗ | ↑2 &], or one of the triplet
S = 1 states, which are symmetric, √12 [| ↑1 & ⊗ | ↓2 & + | ↓1 & ⊗ | ↑2 &], | ↑1 & ⊗ | ↑2 &
(1) (2)
or | ↓1 & ⊗ | ↓2 &. We must therefore choose values of L with the appropriate m! m! mL
symmetry to partner each value of S. To form an antisymmetric state, the two 1 0 1
1 −1 0
electrons must have different values of m! , so the possibilities are as shown
0 −1 −1
right. Inspecting the values of mL we can deduce that L = 1.10 By contrast,
to form a symmetric total angular momentum state, the two electrons may (1) (2)
have any values of m! , leading to the possibilities shown right. Inspecting the m! m! mL
1 1 2
values of mL we infer that L = 2 or 0.
1 0 1
We must therefore take S = 1 with L = 1 and S = 0 with L = 2 or 0. 1 −1 0
Finally, to account for the fine structure, we note that the states with S = 1 0 0 0
and L = 1 can be combined into a single J = 0 state, three J = 1 states, and 0 −1 −1
five J = 2 states leading to the terms 3 P0 , 3 P1 , and 3 P2 respectively. Similarly −1 −1 −2
the S = 0, L = 2 state can be combined to give five J = 2 states, 1 D2 , while the
S = 0, L = 0 state gives the single J = 0 state, 1 S0 . Altogther we recover the E /cm−1
1 + 3 + 5 + 5 + 1 = 15 possible states (cf. Eq. (9.6) with the ordering in energy 1
S0 20649
given by Hund’s rules (shown to the right). The experimental energy values 1
D2 10195
are given using the conventional spectroscopic units of inverse wavelength.
3
P2 43
Note that the Landé interval rule is approximately obeyed by the fine structure
3
P1 16
3
P0 0
triplet, and that the separation between L and S values caused by the electron-
electron repulsion is much greater than the spin-orbit effect.
In an excited state of carbon, e.g. (2p)1 (3p)1 , the electrons are no longer
equivalent, because they have different radial wavefunctions. So now one can
combine any of S = 0, 1 with any of L = 0, 1, 2, yielding the following terms
(in order of increasing energy, according to Hund’s rules):
3
D1,2,3 3
P0,1,2 3
S1 1
D2 1
P1 1
S0 .

For nitrogen, the electron configuration is given by (1s)2 (2s)2 (2p)3 . The
maximal value of spin is S = 3/2 while L can take values 3, 2, 1 and 0. Since
10
This result would also be apparent if we recall the that angular momentum states are
eigenstates of the parity operator with eigenvalue (−1)L . Since there are just two electrons,
this result shows that both the L = 0 and L = 2 wavefunction must be symmetric under
exchange.

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9.3. COUPLING SCHEMES 105

the spin wavefunction (being maximal) is symmetric, the spatial wavefunction

must be completely antisymmetric. This demands that all three states with
m! = 1, 0, −1 must be involved. We must therefore have L = 0, leading to
J = 3/2 and the term, 4 S3/2 .

$ Exercise. Construct the L = 0 state involving the addition of three ' = 1

angular momentum states. Hint: make use of the total antisymmetry condition.

As a final example, let us consider the ground state of oxygen, which has
electron configuration (2p)4 . Although there are four electrons in the (2p)
subshell, the maximum value of S = 1. This is because there are only three
available values of m! = ±1, 0, and therefore one of these must contain two
electrons with opposite spins. Therefore, the maximum value of mS = 1,
achieved by having electrons with ms = + 12 in both the other m! states. By
pursuing this argument, it is quite easy to see that the allowed values of L, S Level scheme of the carbon
atom (1s)2 (2s)2 (2p)2 . Draw-
and J are the same as for carbon (2p)2 . This is in fact a general result – the
ing is not to scale. On the
allowed quantum numbers for a subshell with n electrons are the same as for left the energy is shown with-
that of a subshell with n “holes”. Therefore, the energy levels for the oxygen out any two-particle interaction.
ground state configuration are the same as for carbon, except that the fine The electron-electron interaction
structure multiplet is inverted, in accordance with Hund’s third rule. leads to a three-fold energy split-
ting with L and S remaining
good quantum numbers. Spin-
9.3.2 jj coupling scheme
orbit coupling leads to a further
When relativitic effects take precedence over electron interaction splitting of the states with J re-
6 effects, we maining a good quantum num-
must start by considering the eigenstates of Ĥ0 + Ĥ2 = Ĥ0 + i ξi (ri )L̂i · Ŝi .
ber. Finally on the right, the lev-
These must be eigenstates of Ĵ2 as before, because of the overall rotational els show Zeeman splittings in an
invariance, and also of Ĵ2i for each electron. Therefore, in this case, the cou- external magnetic field. In this
pling procedure is to find the allowed j values of individual electrons, whose case, the full set of 15 levels be-
energies will be separated by the spin-orbit interaction. Then these individual come non-degenerate.
j values are combined to find the allowed values of total J. The effect of the
residual Coulomb interaction will be to split the J values for a given set of js.
Sadly, in this case, there are no simple rules to parallel those of Hund.
As an example, consider a configuration (np)2 in the jj coupling scheme, to
be compared with the example of carbon which we studied in the LS scheme.
Combining s = 1/2 with ' = 1, each electron can have j = 1/2 or 3/2. If
the electrons have the same j value, they are equivalent, so we have to take
care of the symmetry of the wavefunction. We therefore have the following
possibilities:

$ j1 = j2 = 3/2 ⇒ J = 3, 2, 1, 0, of which J = 2, 0 are antisymmetric.

$ j1 = j2 = 1/2 ⇒ J = 1, 0, of which J = 0 is antisymmetric.

$ j1 = 1/2, j2 = 3/2 ⇒ J = 2, 1.

In jj coupling, the term is written (j1 , j2 )J , so we have the following terms in

our example:

(1/2, 1/2)0 (3/2, 1/2)1 (3/2, 1/2)2 (3/2, 3/2)2 (3/2, 3/2)0

in order of increasing energy. Note that both LS and jj coupling give the same
values of J (in this case, two states with J = 0, two with J = 2 and one with
J = 1) and in the same order. However, the pattern of levels is different; in
LS coupling we found a triplet and two singlets, while in this ideal jj scenario,
we have two doublets and a singlet. The sets of states in the two coupling

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9.4. ATOMIC SPECTRA 106

schemes must be expressible as linear combinations of one another, and the

physical states for a real atom are likely to differ from either approximation.
In fact, this idealized form of jj coupling is not seen in the heaviest such
atom in the periodic table, lead (6p)2 . However, it is seen in some highly
ionized states, for example in Cr18+ , which has the same electron configu-
ration (2p)2 as carbon, but where, because of the larger unscreened charge
on the nucleus, the electrons are moving more relativistically, enhancing the
spin-orbit effect. However, a classic example of the transition from LS to jj
coupling is seen in the series C-Si-Ge-Sn-Pb in the excited states (2p)(3s),
(3p)(4s), · · · (6p)(7s) (see figure right). Here, the electrons are not in the same
subshell, so their wavefunctions overlap less, and the Coulomb repulsion is
reduced compared to the spin-orbit interaction. Analysing this situation in
the LS coupling approximation, one expects a triplet and a singlet:
3
P0,1,2 1
P1 ,

while in the jj scheme one expects two doublets:

(1/2, 1/2)0,1 (1/2, 3/2)2,1 .

Experimentally, C and Si conform to the LS expectation and Pb to the jj

scheme, while Ge and Sn are intermediate.

9.4 Atomic spectra

Atomic spectra result from transitions between different electronic states of
an atom via emission or absorption of photons. In emission spectra, an
atom is excited by some means (e.g. thermally through collisions, or by an
electric discharge), and one observes discrete spectral lines in the light emitted
as the atoms relax. In absorption spectra, one illuminates atoms using a
broad waveband source, and observes dark absorption lines in the spectrum
of transmitted light. Of course the atoms excited in this process subsequently
decay by emitting photons in random directions; by observing in directions
away from the incident light this fluorescence radiation may be studied. The
observation of these spectral lines is an important way of probing the atomic
energy levels experimentally. In the case of optical spectra and the nearby
wavebands, the excited states responsible generally involve the excitation of
a single electron from the ground state to some higher level. In some cases,
it may simply involve a different coupling of the angular momenta within the
same electron configuration. These are the kinds of excitations which we are
about to discuss. However, other types of excitations are also possible. For
example, X-ray emission occurs when an electron has been removed from one
of the innermost shells of a heavy atom; as electrons cascade down to fill the
hole, high energy photons may be emitted.
The basic theory governing stimulated emission and absorption, and spon-
taneous emission of photons will be outlined in detail when we study radiative
transitions in chapter 13. Here we must anticipate some of the basic con-
clusions of that study. In the electric dipole approximation, the rate of
transitions is proportional to the square of the matrix element of the electric
dipole operator between the initial and final states, |%ψf |d̂|ψi &|2 . In addition,
the rate of spontaneous transitions is proportional to ω 3 , where ω = |Ef − Ei |
denotes the energy separation between the states.
The form of the dipole operator, d̂ means that the matrix elements may
vanish identically. This leads to a set of selection rules defining which tran-
sitions are allowed. Here we consider the simplest case of a single electron, but

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9.4. ATOMIC SPECTRA 107

the principles can be generalized. Referring to chapter 13 for a more detailed

discussion, one finds that, for a transition to take place:

$ Parity must change;

$ ∆J = ±1, 0 (but 0 → 0 is not allowed) and ∆MJ = ±1, 0 .

Atomic states are always eigenstates of parity and of total angular momentum,
J, so these selection rules can be regarded as absolutely valid in electric dipole
transitions. It should be emphasized again, though, that the electric dipole
approximation is an approximation, and higher order processes may occur,
albeit at a slower rate, and have their own selection rules.
In specific coupling schemes, further selection rules may apply. In the case
of ideal LS coupling, we also require:

$ ∆S = 0 and ∆MS = 0;

$ ∆L = ±1, 0 (but 0 → 0 is not allowed) and ∆ML = ±1, 0;

$ and ∆'i = ±1 if only electron i is involved in the transition.

In LS coupling, the states are eigenstates of total spin; since the dipole operator
does not operate on the spin part of the wavefunction, the rules on ∆S and
∆MS follow straightforwardly. This, and the absolute rules relating to J,
imply the rules for L and ML . The rule for ∆'i follows from the parity change
rule, since the parity of the atom is the product of the parities of the separate
electron wavefunctions, given by (−1)!i . However, since LS coupling is only
an approximation, these rules should themselves be regarded as approximate.
With this preparation, we now turn to the consequences of the selection rules
on the atomic spectra of atoms.

9.4.1 Single electron atoms

In this context, “single electron atoms” refer to atoms whose ground state
consists of a single electron in an s level, outside closed shells; it is this electron
which is active in optical spectroscopy. Our discussion therefore encompasses
the alkali metals, such as sodium, and also hydrogen. We take sodium,
whose ground state configuration is (3s)1 , as our example:

$ The ground state has term 2 S1/2 . The excited states are all doublets
with J = L ± 1/2, except for the s states, which are obviously restricted
to J = 1/2.

$ The parity is given by (−1)!i , so the allowed transitions involve changes

in ' by ±1 unit, i.e. s ↔ p, p ↔ d, d ↔ f , etc. Changes of more than
one unit in ' would fall foul of the ∆J rule.

$ The s ↔ p transitions are all doublets. All the doublets starting or

ending on a given p state have the same spacing in energy. The transition
3s ↔ 3p gives rise to the familiar yellow sodium “D-lines” at 589 nm
(see right).

$ The p ↔ d transitions involve two doublets, 2 P1/2,3/2 and 2 D3/2,5/2 .

However, the 2 P1/2 ↔2 D5/2 transition is forbidden by the ∆J rule, so
the line is actually a triplet. In practice, the spin-orbit interaction falls
quite rapidly with increasing ' (and with increasing n) as the effect of
screening increases, so that the effect of the 2 D3/2,5/2 splitting may not
be resolved experimentally.

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9.4. ATOMIC SPECTRA 108

$ As n increases, the energy levels approach (from below) those for hy-
drogen, because the nuclear charge is increasingly effectively screened
by the inner electrons. This happens sooner for the higher ' values, for
which the electron tends to lie further out from the nucleus.

$ In an absorption spectrum, the atoms will start from the ground state,
so only the 3s → np lines will be seen. In emission, the atoms are excited
into essentially all their excited levels, so many more lines will be seen
in the spectrum.

The comments above for sodium also apply for hydrogen, except that, in this
case, (2s, 2p), (3s, 3p, 3d), etc. are degenerate. One consequence is that the 2s
state in hydrogen is metastable – it cannot decay to the only lower lying level
(1s) by an electric dipole transition. In fact its favoured spontaneous decay
is by emission of two photons; a process which is described by second-order
perturbation theory. In practice, hydrogen atoms in a 2s state are more likely
to deexcite through collision processes. During an atomic collision, the atoms
are subject to strong electric fields, and we know from our discussion of the
Stark effect that this will mix the 2s and 2p states, and decay from 2p to 1s
is readily possible.

9.4.2 Helium and alkali earths

We next discuss atoms whose ground state consists of two electrons in an s
level. Our discussion therefore covers helium (1s)2 , and the alkali earths:
beryllium (2s)2 , magnesium (3s)2 , calcium (4s)2 , etc. We start with helium.

$ The ground state has term 1 S0 . The excited states are of the form
(1s)(n') (the energy required to excite both of the 1s electrons to higher
states is greater than the first ionization energy, and therefore these
form discrete states within a continuum of ionized He+ +e− states). The
excited states can have S = 0 or S = 1, with S = 1 lying lower in energy
(Hund).

$ The LS coupling approximation is pretty good for helium, so the ∆S = 0

selection rule implies that the S = 0 and S = 1 states form completely
independent systems as far as spectroscopy is concerned.

$ The lines in the S = 0 system are all singlets. They can be observed
in emission, and those starting from the ground state can be seen in
absorption.

$ The lines in the S = 1 system are all multiplets. They can be observed
in emission only. Transitions of the form 3 S1 ↔3 P2,1,0 are observed as
triplets, spaced according to the Landé interval rule. Transitions of the
form 3 P2,1,0 ↔3 D3,2,1 are observed as sextuplets, as is easily seen by
application of the ∆J = ±1, 0 rule. Actually, as mentioned above, the
fine structure is a little more subtle in the case of helium.

The alkali earths follow the same principles. In the case of calcium, the
triplet 4p state is the lowest lying triplet state, and therefore metastable. In
fact a faint emission line corresponding to the 3 P1 →1 S0 decay to the ground
state may be observed; this violates the ∆S = 0 rule, and indicates that the LS
coupling approximation is not so good in this case. A more extreme example is
seen in Mercury, ground state (6s)2 (5d)10 . Excited states involving promotion
of one of the 6s electrons to a higher level can be treated just like the alkali

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9.5. ZEEMAN EFFECT 109

earths. In this case the “forbidden” 3 P1 →1 S0 is actually a prominent feature

of the emission spectrum in the visible, implying a significant breakdown of
the LS approximation.

9.4.3 Multi-electron atoms

Similar principles can be used to make sense of the spectra of more complicated
atoms, though unsurprisingly their structure is more complex. For example,
carbon, with ground state (2s)2 (2p)2 , corresponds to terms 3 P0,1,2 , 1 D2 and
1 S as discussed above. The excited states are of the form (2s)2 (2p)1 (n')1 ,
0
and can be separated into singlets and triplets, and in addition excitations
of the form (2s)1 (2p)3 can arise. Nitrogen, with ground state (2s)2 (2p)3 , has
three unpaired electrons, so the ground state and excited states form doublets
(S = 1/2) and quartets (S = 3/2) with correspondingly complex fine structure
to the spectral lines.

9.5 Zeeman effect

9.5.1 Single-electron atoms
Before leaving this chapter on atomic structure, we are now in a position to
revisit the question of how atomic spectra are influenced by a magnetic field.
To orient our discussion, let us begin with the study of hydrogen-like atoms
involving just a single electron. In a magnetic field, the Hamiltonian of such
a system is described by Ĥ = Ĥ0 + Ĥrel. + ĤZeeman , where Ĥ0 denotes the
non-relativistic Hamiltonian for the atom, Ĥrel. incorporates the relativistic
corrections considered earlier in the chapter, and
eB
ĤZeeman = − (L̂z + 2Ŝz ) ,
2mc
denotes the Zeeman energy associated with the coupling of the spin and orbital
angular momentum degrees of freedom to the magnetic field. Here, since
we are dealing with confined electrons, we have neglected the diamagnetic
contribution to the Hamiltonian. Depending on the scale of the magnetic field,
the spin-orbit term in Ĥrel. or the Zeeman term may dominate the spectrum
of the atom.
Previously, we have seen that, to leading order, the relativistic corrections
lead to a fine-structure energy shift of
! " ! "
1 2 Zα 4 3 n
∆En,j = mc
rel.
− ,
2 n 4 j + 1/2
for states |n, j = ' ± 1/2, mj , '&. For weak magnetic fields, we can also treat
the Zeeman energy in the framework of perturbation theory. Here, although
states with common j values (such as 2S1/2 and 2P1/2 ) are degenerate, the
two spatial wavefunctions have different parity (' = 0 and 1 in this case),
and the off-diagonal matrix element of ĤZeeman coupling these states vanishes.
We may therefore avoid using degenerate perturbation theory. Making use of
the relation (exercise – refer back to the discussion of the addition of angular
momenta and spin in section 6.4.2),
!mj
%n, j = ' ± 1/2, mj , '|Sz |n, j = ' ± 1/2, mj , '& = ± ,
2' + 1
we obtain the following expression for the first order energy shift,
! "
1
∆Ej=!±1,mj ,! = ' ± 1/2, mj , '& = µB Bmj 1 ±
Zeeman
,
2' + 1

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9.5. ZEEMAN EFFECT 110

Figure 9.4: The well known doublet which is responsible for the bright yellow light
from a sodium lamp may be used to demonstrate several of the influences which
cause splitting of the emission lines of atomic spectra. The transition which gives
rise to the doublet is from the 3p to the 3s level. The fact that the 3s state is lower
than the 3p state is a good example of the dependence of atomic energy levels on
orbital angular momentum. The 3s electron penetrates the 1s shell more and is less
effectively shielded than the 3p electron, so the 3s level is lower. The fact that there
is a doublet shows the smaller dependence of the atomic energy levels on the total
angular momentum. The 3p level is split into states with total angular momentum
J = 3/2 and J = 1/2 by the spin-orbit interaction. In the presence of an external
magnetic field, these levels are further split by the magnetic dipole energy, showing
dependence of the energies on the z-component of the total angular momentum.

where µB denotes the Bohr magneton. Therefore, we see that all degenerate
levels are split due to the magnetic field. In contrast to the “normal” Zeeman
effect, the magnitude of the splitting depends on '.

$ Info. If the field is strong, the Zeeman energy becomes large in comparison
with the spin-orbit contribution. In this case, we must work with the basis states
|n, ', m! , ms & = |n, ', m! & ⊗ |ms & in which both Ĥ0 and ĤZeeman are diagonal. Within
first order of perturbation theory, one then finds that (exercise)
! "4 ! "
1 Zα 3 n nm! ms
∆En,!,m! ,ms = µB (m! + ms ) + mc2 − − ,
2 n 4 ' + 1/2 '(' + 1/2)(' + 1)

the first term arising from the Zeeman energy and the remaining terms from Ĥrel. . At
intermediate values of the field, we have to apply degenerate perturbation theory to
the states involving the linear combination of |n, j = '±1/2, mj , '&. Such a calculation
reaches beyond the scope of these lectures and, for details, we refer to the literature
(see, e.g., Ref. [6]. Let us instead consider what happens in multi-electron atoms.

9.5.2 Multi-electron atoms

For a multi-electron atom in a weak magnetic field, the appropriate unper-
turbed states are given by |J, MJ , L, S&, where J, L, S refer to the total
angular momenta. To determine the Zeeman energy shift, we need to deter-
mine the matrix element of Ŝz . To do so, we can make use of the following

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9.5. ZEEMAN EFFECT 111

argument. Since 2L̂ · Ŝ = Ĵ2 − L̂2 − Ŝ2 , this operator is diagonal in the basis of
states, |J, MJ , L, S&. Therefore, the matrix element of the operator (exercise,
hint: recall that [Ŝi , Ŝj ] = i!"ijk Ŝk and [L̂i , Ŝk ] = 0),

−i!Ŝ × L̂ ≡ Ŝ(L̂ · Ŝ) − (L̂ · Ŝ)Ŝ

must vanish. Moreover, from the identity [L̂ · Ŝ, Ĵ] = 0, it follows that the
matrix element of the vector product,

−i!(Ŝ × L̂) × Ĵ = Ŝ × Ĵ(L̂ · Ŝ) − (L̂ · Ŝ)Ŝ × Ĵ ,

must also vanish. If we expand the left hand side, we thus find that the matrix
element of
L̂=Ĵ−Ŝ
(Ŝ × L̂) × Ĵ = L̂(Ŝ · Ĵ) − Ŝ(L̂ · Ĵ) = Ĵ(Ŝ · Ĵ) − ŜĴ2 ,

also vanishes. Therefore, it follows that %ŜĴ2 & = %Ĵ(Ŝ · Ĵ)&, where the expec-
tation value is taken over the basis states. Then, with Ŝ · Ĵ = 12 (Ĵ2 + Ŝ2 − L̂2 ),
we have that
J(J + 1) + S(S + 1) − L(L + 1) Figure 9.5: In the weak field
%Ŝz & = %Jˆz & . case, the vector model (top) im-
2J(J + 1)
plies that the coupling of the or-
As a result, we can deduce that, at first order in perturbation theory, the bital angular momentum L to
energy shift arising from the Zeeman term is given by the spin angular momentum S
is stronger than their coupling
∆EJ,MJ ,L,S = µB gJ MJ B , to the external field. In this
case where spin-orbit coupling is
where dominant, they can be visual-
ized as combining to form a to-
J(J + 1) + S(S + 1) − L(L + 1) tal angular momentum J which
gJ = 1 + , then precesses about the mag-
2J(J + 1) netic field direction. In the
strong field case, S and L cou-
denotes the effective Landé g-factor, which lies between 1 and 2. Note that, ple more strongly to the exter-
in the special case of hydrogen, where S = 1/2 and J = L ± 1/2, we recover nal magnetic field than to each
our previous result. The predicted Zeeman splitting for sodium is shown in other, and can be visualized as
figure 9.4. independently precessing about
the external field direction.
$ Info. In the strong field limit, where the influence of Zeeman term domi-
nates, the appropriate basis states are set by |L, ML , S, MS &, in which the operators
L̂2 , L̂z , Ŝ 2 , Ŝz , and ĤZeeman are diagonal. In this case, the energy splitting takes the
form
! "4
1 Zα nML MS
∆EL,ML ,S,MS = µB B(ML + 2MS ) + mc2 ,
2 n '(' + 1/2)(' + 1)

where the second term arises from the spin-orbit interaction.

Advanced Quantum Physics

Chapter 10

From molecules to solids

In the previous section, we studied the quantum mechanics of multi-electron

– the subject of atomic physics. In this section, we will begin to explore
how these concepts get translated into systems with many atoms, from simple
molecular structures to the solid state. As with atomic physics, the subjects
of molecular and solid state physics represent fields in their own right and
it would fanciful to imagine that we could do more than touch on the basic
principles. Nevertheless, in establishing the foundations of these subjects,
we will see two things: firstly, by organising the heirarchy of approximation
schemes, much be can be understood about the seemingly complex quantum
dynamics of many-particle systems. Secondly, we will find that constraints
imposed by symmetries (such as translation) allow a simple phenomenology
to emerge from complex solid state systems. We begin our discussion with the
molecular system.
A molecule consists of electrons moving in the complicated potential set J. Robert Oppenheimer 1904-
up by all the constituent electric charges. Even in classical mechanics, it 1967
An American
would be extremely difficult to solve the equations of motion of the internal theoretical physi-
molecular degrees of freedom. Fortunately, for most purposes, we can treat cist best known
for his role as the
the motion of the electrons and nuclei separately, due to their very different scientific director
masses. As the forces on a nucleus are similar in magnitude to those that act of the Manhat-
on an electron, so the electrons and nuclei must have comparable momenta. tan Project: the
World War II
Therefore the nuclei are typically moving much more slowly than the electrons. effort to develop
In studying the motion of the electrons, we can therefore treat the nuclei as the first nuclear weapons at Los
Alamos National Laboratory. In
being “nailed down” in fixed positions. Conversely, in studying the nuclear reference to the Trinity test in New
motion (vibrations and rotations of the molecule) we can assume, as a first Mexico, where his Los Alamos team
first tested the bomb, Oppenheimer
approximation, that the electrons adjust instantly to changes in the molecular famously recalled the Bhagavad
conformation defined by the positions of the nuclei. This picture forms the Gita: “If the radiance of a thousand
basis of the Born-Oppenheimer approximation. suns were to burst at once into the
sky, that would be like the splendor
In quantum mechanics, the wavefunction of a molecule, Ψ({rn }, {RN }), is of the mighty one.” and “Now I
a function of the positions of all the electrons and nuclei, and the Hamiltonian am become Death, the destroyer of
worlds.” As a scientist, Oppenheimer
has the form is remembered most for being the
chief founder of the American school
! p̂2 ! p̂2 of theoretical physics while at the
n
Ĥ = + N
+ V ({rn }, {RN }) , University of California, Berkeley. As
n
2m e 2m N director of the Institute for Advanced
N
Study he held Einstein’s old position
of Senior Professor of Theoretical
where, as usual, the momentum operators, p̂n and p̂N , act only on the cor- Physics. Oppenheimer’s notable
achievements in physics include the
responding coordinates. Here we have labelled electrons by lower case letters Born-Oppenheimer approximation,
n = 1, 2, · · · to distinguish them from nuclei which are denoted by capitals, work on electron-positron theory,
N = a, b, · · ·. The statement that the electrons and nuclei have comparable the Oppenheimer-Phillips process,
quantum tunneling, special relativity,
momenta translates into the fact that ∇2n Ψ and ∇2N Ψ will be comparable. quantum mechanics, quantum field
Therefore the second term in the Hamiltonian above, the sum over nuclear theory, black holes, and cosmic rays.

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10.1. THE H+
2 ION 113

kinetic energies, can be neglected as a first approximation when we solve for

the dependence of Ψ on the electron position vectors {rn }.
In the Born-Oppenheimer approximation, the time-independent Schrödinger
equation for the electronic motion is therefore given by
" #
! !2 ∇2
n
− + V ({rn }, {RN }) ψk ({rn }, {RN }) = Ek ({RN }) ψk ({rn }, {RN }) ,
n
2m e

where the eigenfunctions ψk , with k = 0, 1, 2, · · ·, describe the electronic

ground state and excited states with the nuclei nailed down at positions
Ra , Rb , . . .; Ek are the corresponding energy levels. Notice that the nuclear
positions appear as parameters in ψk and Ek . As the molecular conformation
is varied by changing Ra , Rb , . . ., the ground state energy E0 follows a curve
called the molecular potential energy curve and the minimum of this curve
defines the equilibrium conformation of the molecule. We shall discuss later
how the molecular potential energy curve can be used to predict the vibra-
tional and rotational energy levels of the molecule when we go beyond the
approximation that the nuclei are nailed down.

10.1 The H+
2 ion

The simplest system that exhibits molecular properties is the hydrogen ion
H+2 , which consists of two protons with positions Ra , Rb and one electron at
r. With the potential energy
$ %
e2 1 1 1
V (r, Ra , Rb ) = − − ,
4π#0 |Ra − Rb | |r − Ra | |r − Rb |

the Schrödinger equation takes the form,

& 2 2 '
! ∇r
− + V (r, Ra , Rb ) ψ(r; Ra , Rb ) = Eψ(r; Ra , Rb ) .
2me

Although this equation can actually be solved exactly using elliptical polar
coordinates, it will be more instructive for our purposes to seek an approximate
method of solution. Since there is no obvious parameter in which to develop
a perturbative expansion, we will instead follow a variational route to explore
the low energy states of system.
If the electron is close to one of the protons, one would expect the other
proton to have a small influence on its dynamics, and that the wavefunction
in this region would be close to that of a hydrogen atomic orbital. Therefore,
in seeking the ground state of the H+ 2 ion, we may take a trial wavefunction
that is a linear combination of the ground state (1s) wavefunctions centred on
the two protons,

ψ(r; Ra , Rb ) = αψa (r; Ra ) + βψb (r; Rb ) ,

where ψa,b = (πa30 )−1/2 exp[−|r − Ra,b |/a0 ], represents the corresponding hy-
drogenic wavefunction with a0 the atomic Bohr radius. In this case, the co-
efficients α and β can be taken as real. The variational expression to be
minimized in order to estimate the ground state energy is given by

#ψ| Ĥ |ψ$ α2 Haa + β 2 Hbb + 2αβHab

#E$ = =
#ψ|ψ$ α2 + β 2 + 2αβS

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10.1. THE H+
2 ION 114

where Haa = #ψa |Ĥ|ψa $ = Hbb = #ψb |Ĥ|ψb $, and Hab = #ψa |Ĥ|ψb $ = #ψb |Ĥ|ψa $.
Note that the matrix elements Haa = Hbb because Ĥ is symmetric with re-
spect to Ra and Rb . Moreover, since ψa and ψb are not orthogonal we have
to introduce the overlap integral, S = #ψa |ψb $, which measures the overlap
between the two atomic wavefunctions. In fact we can simplify this expres-
sion further, because the potential is symmetric about the mid-point between
the two protons. The wavefunction must therefore be either symmetric or
antisymmetric, α = ±β, and hence,
Haa ± Hab
E0 ≤ #E$ = .
1±S
The matrix elements in this expression can be evaluated in closed form, though
the calculation is rather tedious.1
We have, therefore, found two possible wavefunctions for the H+ 2 ion,

ψa + ψb ψa − ψb
ψg = ( , ψu = ( ,
2(1 + S) 2(1 − S)
−Hab
with energies Eg = Haa1+S+Hab
, Eu = Haa1−S . The subscript g refers to the term
gerade (German for even) used in molecular physics to denote a state that is
even under the operation of inverting the electronic wavefunction through
the centre of symmetry of the molecule, without changing the positions of the
nuclei. Such an inversion changes r → Ra + Rb − r, which interchanges ψa and
ψb . Note that this is not the same as parity inversion, which would also affect
the nuclear coordinates. The ungerade (odd) state is denoted by subscript u.
Note that ψg and ψu are orthogonal, even though ψa and ψb are not. In fact,
ψg and ψu are just the orthonormal states that diagonalize the Hamiltonian,
if we limit ourselves to linear combinations of ψa and ψb . In chemistry, ψg and
ψu are called molecular orbitals and the assumption that they are linear
combinations of atomic stationary states is called the linear combination
of atomic orbitals (LCAO) approximation.
The state ψg has the lower energy, while ψu represents an excited state of
the molecular ion. Physically, the reason for this is that, in the ψg state, the E/eV
two atomic wavefunctions interfere constructively in the region between the 4!
3 Eu + Ry
protons, giving an enhanced electron density in the region where the electron #
is attracted strongly by both protons, which serves to screen the two protons 2 #
$
from each other. Conversely, in ψu we have destructive interference in the 1
region between the protons. If we plot Eg and Eu as functions of the nuclear 0 " R/pm
separation R = |Ra − Rb |, the results are as shown in the figure right. For 100 200 300
–1
both curves, we have plotted E + Ry since −Ry is the ground state energy of %
&
%
–2 %
&
the hydrogen atom. The curve of Eg + Ry in the LCAO approximation has a %% LCAO Eg + Ry
–3 % Exact E + Ry
minimum value of −1.8eV at R = R0 = 130pm, which is the predicted equi- g

librium nuclear separation. The predicted energy required to dissociate the

molecular ion into a hydrogen atom and a free proton is thus 1.8eV. The curve
Molecular potential energy
of Eu + Ry does not have a minimum, suggesting that the odd wavefunction
curves for H2 ion.
+
ψu does not correspond to a bound molecular state.
1
We simply quote the results here:
„ « „ «
R R2 e2 R
S = 1+ + 2 e−R/a0 , Haa = −Ry + 1+ e−2R/a0
a0 3a0 4π"0 R a0
„ « „ «
e2 R e2
Hab = 1+ e−R/a0 + S −Ry + ,
4π"0 a0 a0 4π"0 R

where R = |Ra − Rb | and Ry is the Rydberg constant, the binding energy of the Hydrogen
atom in its ground state.

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10.1. THE H+
2 ION 115

As the variational method provides an upper limit on the ground state

energy, it is no surprise that the true molecular potential energy curve (shown
dotted) lies below the LCAO one. The true values of the equilibrium sep-
aration and dissociation energy are 106pm and 2.8eV respectively. Clearly
the LCAO wavefunction ψg is not a very accurate approximation to the true
ground state. We could improve it by introducing further variational param-
eters or additional atomic orbitals. For example, when R becomes very small
the true wavefunction should approach that of a He+ ion; we could include
such a term in the trial function. We could also include an effective charge
parameter in ψa and ψb , which is equivalent to replacing the Bohr radius a0
by a free parameter.
Although not very reliable quantitatively, the LCAO wavefunction ψg does
however exhibit a number of important features of the true ground state: (i)
it is even (g) with respect to inversion of the electron wavefunction; (ii) there
is constructive interference which leads to an enhanced probability of finding
the electron in the region between the two nuclei. These features will be
important when we come to discuss bonding. Since the odd u-states are
orthogonal to the even g-states, and the true ground state is a g-state, the
curve of Eu actually represents an upper limit on the energy of the lowest
u-state. Thus the fact that the curve has no minimum does not really prove
that there are no bound u-states; but this does turn out to be the case. The
LCAO wavefunction ψu shows the characteristic feature of an anti-bonding
state: there is destructive interference in the region between the two nuclei,
so that the electron is actually forced out of the region of overlap of the two
atomic wavefunctions.

& Info. At this stage, it is helpful to introduce some notation to label the
molecular orbitals. Although the wavefunctions ψg,u that we have been discussing
are formed in the LCAO approximation from linear combinations of atomic 1s (n = 1,
' = 0) states, with no orbital angular momentum, they do not themselves necessarily
have zero orbital angular momentum. An ' = 0 state must be proportional to Y00 ,
i.e., it must have no dependence on θ and φ, giving an isotropic probability distri-
bution. But these states are certainly not isotropic: they have a ‘dumbbell’ shape,
concentrated around the two protons. They do not have unique electronic orbital
angular momentum because the operator L̂2 for the electron does not commute with
the Hamiltonian on account of the non-central terms 1/|r − Ra | and 1/|r − Rb | in the
potential.
The only component of L̂ that does commute with these terms is L̂z , provided
we choose the z-axis parallel to the internuclear axis Ra − Rb . Therefore instead of
classifying the states as s, p, d, . . . orbitals according to whether ' = 0, 1, 2, . . ., we
call them σ, π, δ, . . . orbitals according to whether Λ = 0, 1, 2, . . ., where Λ ≡ |m! |.
A subscript u or g denotes whether the state is even or odd under inversion; this
notation can be applied to all homonuclear diatomic molecules, in which the potential
is symmetric about the median plane of the molecule. Thus the ground state of
the hydrogen molecular ion is σg and the corresponding odd state is σu∗ , where the
star signifies an antibonding orbital. In the LCAO approximation used above, these
molecular orbitals are linear combinations of 1s atomic orbitals and so they can be
written as 1sσg and 1sσu∗ . To get some insight into how this denotation applies, it is
helpful to refer to the figures on the right.

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10.2. THE H2 MOLECULE 116

Approximation B.E./eV R0 /pm

Experiment 4.75 74.1
MO fixed charge 2.70 85.2
MO variable charge 3.49 73.0
VB variable charge 3.78 74.6
Variable λ and charge 4.03 75.7
13 variable parameters 4.72 74.1

Table 10.1: Binding energy and equilibrium nuclear separation of the hydrogen
molecule in various approximations.

10.2 The H2 Molecule

We now turn to consider the hydrogen molecule. One might imagine that this
would be a trivial extension of the H+2 ion, but in fact several new features
arise when we consider this simple molecule. For two electrons with positions
r1,2 and two protons at Ra,b , in the Born-Oppenheimer approximation, the
Hamiltonian is given by
& '
!2 ) 2 * e2 1 1 1 1 1 1
Ĥ = − ∇r 1 + ∇ r 2 +
2
+ − − − − ,
2me 4π#0 rab r12 r1a r1b r2a r2b
where r1b = |r1 − Rb |, etc. This is just the sum of two Hamiltonians for
e2
H+2 ions, plus the additional term 4π"0 ( r12 − rab ). It is plausible that the
1 1

expectation values of 1/r12 and 1/rab will be comparable and therefore the
extra term can be treated as a perturbation. Thus, as a first approximation
we neglect it and assign each electron to one of the H+ 2 molecular orbitals
defined above. There are four ways of filling the two orbitals σg and σu∗ , which
we can represent by

ψg (r1 )ψg (r2 ), ψg (r1 )ψu∗ (r2 ), ψu∗ (r1 )ψg (r2 ), ψu∗ (r1 )ψu∗ (r2 ) .

Of these, we would expect the first to be the ground state.

However, at this stage, we have given no consideration to the constraints
imposed by particle statistics. In fact, since the electrons are identical fermions,
the wavefunction must be antisymmetric with respect to their interchange.
Taking into account the spin degree of freedom, for both electrons to occupy
the bonding σg molecular orbital, they must must have opposite spins and
occupy the singlet spin state, X0,0 = √12 (χ+ (1)χ− (2) − χ− (1)χ+ (2)).
If we calculate the energy of the state ψg (r1 )ψg (r2 )X0,0 as a function of the
nuclear separation R, the minimum ground state energy occurs at R0 = 85pm
and corresponds to a binding energy of 2.7eV. The true molecule is smaller
and more tightly bound. Allowing for more variation in the atomic orbitals, in
the form of a variable effective charge, gives an equilibrium value of R0 much
closer to experiment, but a binding energy that is still not high enough (see
Table 10.2). The reason is that the σg2 configuration alone is not a very good
representation of the ground state. To understand why, consider the following.
If we multiply out the spatial part of the σg2 wavefunction in the LCAO
approximation, we see that it has a rather strange form,

ψg (r1 )ψg (r2 ) ∝ [ψa (r1 )ψb (r2 ) + ψb (r1 )ψa (r2 )] + [ψa (r1 )ψa (r2 ) + ψb (r1 )ψb (r2 )] .

The terms in the first square bracket correspond to the two electrons being
shared between the two hydrogen atoms. This is the covalent bonding pic-
ture of the bound state. In the other square bracket, however, both electrons

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10.2. THE H2 MOLECULE 117

are assigned to the same atom, corresponding to ionic bonding. Since all the
terms have equal coefficients, the ionic and covalent contributions are equal,
which seems rather constraining, if not implausible. For example, it means
that, when the two protons are pulled apart, the system is just as likely to be
found to consist of an H+ and an H− ion as two neutral atoms.
If we go to the pure valence bonding (VB) approximation and drop the
ionic part of the wavefunction altogether, we find that the predicted binding
energy and nuclear separation are both improved (see Table 10.2). Including
a small parameter λ for the amplitude of the ionic component, i.e., taking

ψ V B ∝ [ψa (r1 )ψb (r2 ) + ψb (r1 )ψa (r2 )] + λ[ψa (r1 )ψa (r2 ) + ψb (r1 )ψb (r2 )] ,

we find that the variational method gives an optimal value of λ of about

1/6, meaning only about a 3% probability of finding the ionic configuration.
Still, even with this refinement, the agreement with experiment is far from
perfect. However, this doesn’t that mean quantum mechanics is failing; by
taking enough free parameters in the trial function an excellent result can be
obtained, as shown in the Table.

& Info. As mentioned above, there are four possible ways of putting two electrons
into the 1sσg and 1sσu∗ molecular orbitals. From these four two-electron states we
can make three states that are symmetric under interchange of the positions of the
electrons, all of which need to be combined with the antisymmetric spin state X0,0 ,
1
Σg : X0,0 σg (r1 )σg (r2 )
√
1
Σu : X0,0 [σg (r1 )σu∗ (r2 ) + σu∗ (r1 )σg (r2 )]/ 2
1
Σg : X0,0 σu∗ (r1 )σu∗ (r2 ) .

In addition we can make a triplet of states from an antisymmetric spatial wavefunction

and the symmetric triplet spin states X1,mS (mS = 0, ±1),
√
3
Σu : X1,mS [σg (r1 )σu∗ (r2 ) − σu∗ (r1 )σg (r2 )]/ 2 .

We have introduced to the left of these equations a new notation, called the E
molecular term, to describe the overall quantum numbers of the molecule, all of
!
which must be good quantum numbers because they correspond to operators which
commute with the molecular Hamiltonian. It derives from a historic spectroscopic
notation used in atomic physics. The term is written 2S+1 Λu/g . The prefix 2S + 1
denotes the multiplicity of the total spin state of the electrons, hence 1 for a singlet and
3 for a triplet state. The central greek capital letter represents the magnitude of the H+ +H− σ ∗2 "
total L̂z quantum number, Λ = 0, 1, 2 . . . being represented by Σ, Π, ∆ . . .. In the case u
of the molecular orbitals above based on the 1s atomic orbitals, all the wavefunctions σg2
clearly have zero orbital angular momentum about the internuclear axis and hence H+H !"
R
they are all Σ states. The g or u suffix means even or odd under inversion, and is
only meaningful for homonuclear molecules. Notice that since (±1)2 = +1 we get a
g-state by combining two g or two u-states, and a u-state by combining a g and a
u-state.
In terms of the molecular orbital approach, the VB approximation implies that
Molecular potential energy and
the ground state is not simply the σg2 configuration but rather a mixture of the two
1
Σg states, configuration mixing in H2 .

ψ V B ∝ (1 + λ)(1 + S)σg (r1 )σg (r2 ) − (1 − λ)(1 − S)σu∗ (r1 )σu∗ (r2 ) .

Thus there is configuration mixing in the hydrogen molecule. The two states
can mix because they have the same overall quantum numbers. At large nuclear
separations the energy eigenstates are clearly separated into those that are almost a
pair of neutral atoms and those consisting of an H+ and an H− ion. In the case of
the u-states, we can see by expanding the spatial wave functions that 3 Σu is of the
former type and 1 Σu of the latter. Since these configurations have different resultant

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10.3. FROM MOLECULES TO SOLIDS 118

electron spins they do not mix significantly (just like singlet and triplet states of
atomic helium). Also the u- and g-states are prevented from mixing by their different
inversion symmetry. However, the two 1 Σg configurations have the same electron spin
and symmetry and can mix to give the above covalent-bonded ground state and an
orthogonal excited state that is more ionic.

10.3 From molecules to solids

With these basic principles in hand, we could go on to discuss the orbital and
electronic structure of more complicated molecules. In doing so, we would sink
deeper into the realm of quantum chemistry. Instead, we will use these simple
ideas of molecular bonding to develop a surprisingly versatile and faithful
description of the ordered solid state. With ca. 1023 nuclei and electrons
now involved such an enterprise seems foolhardy. However, we will see that,
by exploiting symmetries, we can capture many of the basic principles of the
solid state.
Let us then consider the electronic structure of an ordered crystalline ar-
ray of equivalent atoms. (The consideration of more complicated periodic
structures would not present conceptual challenges, but would bring unnec-
essary complications to the discussion.) Once again, we can draw upon the
Born-Oppenheimer approximation and focus solely on the motion of electrons
around an otherwise ordered array of nuclei. Even then, we are confronted
with a many-particle Hamiltonian of apparantly great complexity,
! !2 ∇2 ! e2 Ze2 ! e2 e2
n
Ĥ = − − + .
n
2me 4π#0 rnN m,n 4π#0 rmn
n,N

Here the second term represents the interaction of the electrons with the con-
situent nuclei, and the third term involves the electron-electron interaction. In
a physical system, we would have to take into account the influence of further
relativistic corrections which would introducte additional spin-orbit couplings.
To address the properties of such a complex interacting system, we will
have to draw upon many of the insights developed previously. To begin, it is
helpful to partition the electrons into those which are bound to the core and
those which are able to escape the potential of the individual atomic nuclei
and propagate “freely” through the lattice. The electrons which are tightly
bound to the nuclei screen the nuclear charge leading to a modified nuclear
potential, Veff (r). Focussing on those electrons which are free, the effective
+ + e2 e2
Hamiltonian can be written as, Ĥ * n Ĥn + m,n 4π" 0 rmn
, where

!2 ∇2n
Ĥn = − + Veff (rn )
2me
represents the single-particle Hamiltonian experienced by each of the electrons
– i.e. Ĥn describes the motion of an electron moving in a periodic lattice
potential, Veff (r) = Veff (r + R) with R belonging to the set of periodic lattice
vectors.
Despite engineering this approximation, we are still confronted by a chal-
lenging many-particle problem. Firstly, the problem remains coupled through
the electron-electron Coulomb interaction. Secondly, the electrons move in a
periodic potential. However, if we assume that the electrons remain mobile –
the jargon is itinerant, free to propagate through the lattice, they screen each
other and diminish the effect of the Coulomb interaction. Therefore, we can

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10.3. FROM MOLECULES TO SOLIDS 119

proceed by neglecting the Coulomb interaction altogether, when the Hamilto-

nian is said to be free. Of course, we still have to contend with the constraints
placed by Pauli exclusion and wavefunction antisymmetry. But we are now in
the realm of the molecular orbital theory, and can proceed analogously using
the variational LCAO approach.
In particular, we can building a trial wavefunction
+ by combining orbital
states of the single ion, Vion (r), where Veff (r) = R Vion (r − R). As with the
hydrogen molecule, the Hamiltonian for the individual nuclei, Ĥ0 = !2m∇e +
2 2

Vion (r) are associated with a set of atomic orbitals, ψq , characterized by a set of
quantum numbers, q. In the atomic limit, when the atoms are far-separated,
these will mirror the simple hydrogenic states. To find the variational ground
state of the system, we can then build a trial state from a linear combination
of these atomic orbitals. Taking only the lowest orbital, q = 0, into account
we have,
!
ψ(r) = αR ψ(r − R) ,
R

where, as before, αR represent the set of variational coefficients, one for each
site (and, in principle, each atomic orbital if we had taken more than one!).
Once again, we can construct the variational state energy,
+ ∗
#ψ|Ĥ0 |ψ$ R,R" αR HRR" αR"
E= = + ∗ ,
#ψ|ψ$ R,R" αR SRR" αR"
,
where, as before, HRR" = dd rψ ∗ (r − R)Ĥ0 ψ(r − R% ) denote the,matrix ele-
ments of the orbital wavefunction on the Hamiltonian and SRR" = dd rψ ∗ (r−
R)ψ(r − R% ) represent the overlap integrals. Then, varying the energy with
respect to αR∗ , we find that the coefficients obey the secular equation (ex-

ercise)
!
[HRR" − ESRR" ] αR" = 0 .
R"

Note that, if the basis functions were orthogonal, this would just be an eigen-
value equation.

& Exercise. To develop this idea, let us first see how the method relates to
back to the problem of H+
2 : In this case, the secular equation translates to the 2 × 2
matrix equation,
$ %
Haa − E Hab − ES
α = 0,
Hab − ES Haa − ES
where the notation and symmetries of matrix elements follow from section 10.1. As
a result, we find that the states α divide into even and odd states as expected.

Now let us consider a one-dimensional periodic lattice system. If we assume

that the atoms are well-separated, it is evident that both the overlap integrals
and matrix elements will decay exponentially fast with orbital separation. The
dominant contribution to the energy will then derive from matrix elements
coupling only neighbouring states. In this case, the secular equation separates
into the coupled sequence of equations,

(ε − E)αn − (t + ES)(αn+1 + αn−1 ) = 0 ,

for each n, where Hnn = ε denotes the atomic orbital energy, Hn,n+1 =
Hn+1,n = −t is the matrix element between neighbouring states, Sn,n = 1

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10.3. FROM MOLECULES TO SOLIDS 120

and Sn+1,n = Sn+1,n = S. All other matrix elements are exponentially small.
Here we consider a system with N lattice sites and impose the periodic bound-
ary condition, αn+N = αn . The periodicity of the secular equation suggests
a solution of the from αn = √1N eikna , where k = 2πm/N a denote a dis-
crete set of N reciprocal lattice vectors with m integer lying in the range
−N/2 < m ≤ N/2. Substitution confirms that this is a solution with energies
(exercise),

ε − 2t cos(ka)
Ek = .
1 + S cos(ka)

The reciprocal lattice vector k parameterizes a band of states.

Then, according to the LCAO approximation, for a single electron, dis-
tributed throughout the system, the lowest energy state is predicted to be the
uniform state αn = √1N with the energy E0 = ε−2t 1+S . (Here we have assumed
that the matrix element, t is positive – in the atomic limit, consider why this
is a sound assumption.) However, if we suppose that each atom contributes a
non-zero fraction of electrons to the system, we must consider the influence of
Pauli exclusion and particle statistics.
Since the electrons are fermions, each state k can host two electrons in a One dimensional band structure
total spin singlet configuration. The lowest energy state is then obtained by for Ek for S = 0.3, t = 1 and
adding electron pairs sequentially into states of increasing k until all electrons ε = 0. Here we have shown
schematically a band-filling with
are accounted for. If the maximum k value, known as the Fermi wavevector,
kF a = π/2.
kF , lies within the band of states, elementary excitations of the electrons cost
vanishingly small energy leading to metallic behaviour. On the other hand, if
the system is stoichiometric, with each atom contributing an integer number of
electrons, the Fermi wavevector may lie at a band gap between two different
band of states. In this case, the system has a gap to excitations and the
material forms a band insulator.

& Exercise. Consider how the calculation above can be extended to a two-
dimensional square lattice system. What would be the corresponding band dispersion?

& Exercise. In the one-dimensional system, extend the calculation to compute

the electron band structure for a periodic lattice with two atomic orbitals on each
site, one with s-wave symmetry, and another with p-wave. In particular, consider how
the dispersion would change with the orientation of the p state relative to the chain
direction.

& Info. To add flesh to these ideas, let us then consider a simple, but prominent
problem from the realm of quantum condensed matter physics. In recent years, there
has been great interest in the properties of graphene, a single layer of graphite.
Remarkably, high quality single crystals of graphene can be obtained by running
graphite – a pencil! – over an adhesive layer. The resulting electron states of the
single layer compound have been of enormous interest to physicists. To understand
why, let us implement the LCAO technology to explore the valence electron structure
of graphene.
Graphene forms a periodic two-dimensional honeycomb lattice structure with two Atomically resolved STM image
atoms per each unit cell. With an electron configuration 1s2 2s2 2p2 , the two 1s of graphene sheet at 77K.
electrons are bound tightly to the nucleus. The remaining 2s electrons hybridize
with one of the p orbitals to form three sp2 hydridized orbitals. These three orbitals
form the basis of a strong covalent bond of σ orbitals that constitute the honeycomb
lattice. The remaining electron, which occupies the out-of-plane pz orbital, is then

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10.3. FROM MOLECULES TO SOLIDS 121

Figure 10.1: Left: dispersion relation of graphene Ek obtained with the LCAO
approximation. Notice that near the centre of the band, the dispersion becomes
point-like. Around these points, the dispersion takes form of a linear (Dirac) cone.
Right: band structure of a sample of multilayer epitaxial graphene. Linear bands
emerge from the K-points in the band structure. Three “cones” can be seen from
three layers of graphene in the MEG sample.

capable of forming an itinerant band of electron states. It is this band which we now
address.
Once again, let us suppose that the wavefunction of this band involves the basis
of single pz orbital states localized to each lattice site,
!
ψ(r) = [αR ψ1 (r − R) + βR ψ2 (r − R)] .
R

Here the pz orbital wavefunction ψ1 is centred on one of the atoms in the unit cell, and
ψ2 is centred on the other. Once again, taking into account matrix elements involving
only nearest neighbours, the trial wavefunction translates to the secular equation,
(ε − E)αR − (t + ES)(βR + βR−a1 + βR−a2 ) = 0
(ε − E)βR − (t + ES)(αR + αR+a1 + αR+a2 ) = 0 ,
√ √
where the lattice vectors a1 = ( 3/2, 1/2)a and a2 = ( 3/2, −1/2)a, with a the
lattice spacing, are shown in the figure to the right. Note that the off-diagonal matrix
elements involve only couplings between atoms on different sublattices. Once again,
we can make the ansatz that the solutions are of the form of plane waves with αR =
√αk ik·R
N
e and βR = √βN k
eik·R . Notice that, in this case, we must allow for different
relative weights, αk and βk . Substituting, we find that this ansatz is consistent if
(ε − E)αk − (t + ES)fk βk = 0
(ε − E)βk − (t + ES)fk∗ αk = 0
√
where fk = 1+2e−i 3kx a/2 cos(ky a/2). Although this equation can be solved straight-
forwardly, it takes a particularly simple form when the overlap integral between neigh-
bouring sites, S, is neglected. In this case, one obtains,
Ek = ε ± |fk |t .
The corresponding band structure is shown right as a function of k. In particular, one
may note that, at the band centre, the dispersion relation for the electrons becomes
point-like (see Fig. 10.3).
In the half-filled system, where each carbon atom contributes a single electron to
the band, the Fermi level lies precisely at the centre of the band where the dispersion,
Ek is point like. Doping electrons into (or removing electrons from) the system
results in (two copies) of a linear dispersion, Ek * c|k|, where is c is a constant
(velocity). Such a linear dispersion relation is the hallmark of a relativistic particle
(cf. a photon). Of course, in this case, the electrons are not moving at relativistic
velocities. But their properties will mirror the behaviour of relativistic particles. And
herein lies the interest that these materials have drawn.

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10.4. MOLECULAR SPECTRA 122

Finally, let us comment on the influence of the electron-electron interaction

effects that were neglected in our treatment above. In principle, we could adopt
a Hartree or Hartree-Fock scheme to address the effects of electron interaction
in a perturbative manner. Indeed, such a programme would lead to interaction
corrections which would modify the electronic band structure derived above.
It is a surprising yet robust feature of Fermi systems that the properties of the
non-interacting ground state wavefunction remain qualitatively correct over
an unreasonably wide range of interaction strengths.2 This rigidity can be
ascribed to the contraints implied on the nodal structure of the wavefunction
imposed by particle statistics. However, in some cases, the manifestations of
electron interactions translate to striking modifications in the experimental
behaviour leading to effects such as interaction-driven electron localization –
the Mott transition, local moment and itinerant magnetism, quantum Hall
fluids, and superconductivity. Such phases, which by their nature, lie outside
any perturbative scheme built around the non-interacting ground state, form
the field of quantum condensed matter and solid state physics.
With this detour, we now return to the simple molecular system, and
consider the question of excitations and transitions.

10.4 Molecular spectra

In the atomic system, our consideration of radiative transitions was limited
to the problem of electronic transitions between states. In the molecular sys-
tem, the internal structure allows for transitions involving rotational and vi-
brational excitations of the consituent nuclei. As with atoms, electronic
transitions are typically of order eV, and so corresponds to wavelengths in
or near the optical region. However, it is unlikely that an electronic transition
will occur without inducing motion of the nuclei as well, because the equi-
librium distances between the nuclei will be different in the initial and final
electron states. The typical energies of rotational states of molecules are much
smaller than those of electronic excited states, of order !2 /2I, where I is the
molecular moment of inertia. Substituting typical values for the interatomic
spacing and atomic masses, one finds that rotational energies are O(10−4 eV),
corresponding to the far infra-red or microwave regions. Typical energies for
vibrational excitations of molecules are O(10−1 eV) (see section 10.4.2 below),
corresponding to the infra-red waveband.
All of these types of transitions can occur radiatively, i.e. through the
emission or absorption of a photon of the appropriate frequency ν = ∆E/h.3
As in the case of atoms, the most probable radiative transitions are usually
electric dipole transitions. In an electric dipole transition, the photon carries
one unit of angular momentum and negative parity, so there will be the usual
selection rule for the change in the total angular momentum quantum number
of the molecule:

∆J = 0, ±1, but not 0 → 0 ,

accompanied by a change in the parity of the molecular state (which may

impose further restrictions on ∆J).

& Info. In a gas or a liquid, transitions can also be produced by collisions

2
The feature is embodied in the theory of the electron liquid known as Landau’s Fermi
liquid theory.
3
Spectroscopists always quote wavenumbers ν̃ = ν/c instead of frequencies, and measure
them in cm−1 .

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10.4. MOLECULAR SPECTRA 123

between molecules. The appropriate energy change can be provided by excitation or

de-excitation of the other molecule, or as part of the kinetic energy of the collision.
Such non-radiative transitions do not have to obey the selection rules above. Thus,
for example, a molecule in a metastable state, i.e. one that cannot return to the
ground state via an allowed radiative transition, can be de-excited by a collision.
In the absence of any incident radiation or other non-thermal sources of excitation,
collisions will bring about a thermal distribution of molecular energy levels, with the
number of molecules in state i being given by ni ∝ gi exp[− kEBiT ], where gi is the
degeneracy and Ei the energy. At room temperature, kB T ∼ 2 × 10−2 eV, so typically
many rotational states of molecules are excited, but not electronic or vibrational.

To study the motion of nuclei in the Born-Oppenheimer Approx-

imation and the associated types of transitions more formally, we must go
back to the molecular Schrödinger equation considered above. Having found
the electronic eigenfunctions, ψk , in the Born-Oppenheimer approximation,
we can use the completeness property of these functions to express the full
stationary state wavefunction of the molecule as
!
Ψ({rn }, {RN }) = φk ({RN })ψk ({rn }, {RN }) ,
k

where φk represents the nuclear part of the wavefunction. Substituting this

expression into the full time-independent Schrödinger equation, we obtain
 
! !2 ∇2 ! !2 ∇2
− n
− N
+ V ({rn }, {RN }) Ψ({rn }, {RN })
2me 2mN
n=1,2,... N =a,b,...
= EΨ({rn }, {RN }) .

Using the electronic energy levels Ek , we have

 
! ! ! 2 !
− ∇2N + Ek ({RN }) φk ψk = E φk ψk .
2mN
k N =a,b,... k

Now another important aspect of the Born-Oppenheimer approximation

comes into play: the dependence of ψk ({rn }, {RN }), the electronic part of the
wavefunction, on the nuclear coordinates {RN } is weak compared with that
of the nuclear part φk ({RN }). We shall verify this explicitly in section 10.4.2
below. Therefore we can write ∇2N φk ψk * ψk ∇2N φk , to a good approximation.
Using the orthogonality of the ψk s, we can now pick out the k = 0 term, for
example, by multiplying by ψ0∗ and integrating over all electron positions, to
obtain
 
! ! 2
− ∇2 + E0 ({RN }) φ0 = Eφ0 .
2mN N
N =a,b,...

Thus the nuclear part of the wavefunction, φ0 , satisfies a Schrödinger equation

in which the full potential V ({rn }, {RN }) is replaced by the molecular poten-
tial energy curve E0 ({RN }), which we derived earlier in the approximation
that the nuclei were nailed down at positions {RN }. The replacement of the
full potential by E0 ({RN }) in the nuclear Schrödinger equation corresponds
physically to assuming that the electrons react instantly to changes in the
molecular conformation.

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10.4. MOLECULAR SPECTRA 124

10.4.1 Molecular rotation

In general, the Schrödinger equation for the nuclear motion has many solu-
tions, which give the various molecular energy levels for a given electronic con-
figuration. Here, for simplicity, we focus on diatomic molecules which capture
the main features of the general phenomenology. In this case, E0 (R1 , R2 ) =
E0 (R) where R = |R1 − R2 | and the usual separation of variables can be per-
formed. One equation describes the translational motion of the overall centre
of mass, and leads to a continuum of possible energies for a free molecule, or
the usual energies of a particle in a box if it is confined. The equation for the
relative coordinate, R = R1 − R2 , is given by
& 2 '
!
− ∇2R + E0 (R) φ0 = Eφ0 ,
2µ

where µ is the reduced mass of the two atoms. In this case, E0 (R) acts as a
central potential, and the usual separation into angular and radial equations
can be carried out.
The simplest solutions are the purely rotational states, in which the whole
molecule rotates around its centre of mass. The solutions will be the spherical
harmonic functions YJ,mJ . Conventionally the quantum numbers are labelled
J and mJ (mJ taking values J, J − 1, · · · , −J), and the corresponding energy
is given by

!2
EJ = J(J + 1) ,
2I

where I = µR02 is the moment of inertia of the molecule about an axis through
the centre of mass orthogonal to the bond, and R0 is the equilibrium bond
length.
As mentioned earlier, the typical energies of rotational states of molecules
are much smaller than those of electronic excited states. Since molecular
dimensions are determined by the electronic wavefunction, their scale is set by
the Bohr radius a0 . Thus moments of inertia are of order mN a20 and the scale
of rotational energies is !2 /mN a20 . For the electronic states, the uncertainty
relation implies momenta of order !/a0 and hence electron energies around
!2 /me a20 , a factor of mN /me ∼ 104 greater.
To bring about a radiative rotational transition, an emitted or absorbed
photon must interact with the electric dipole moment of the molecule. Since
the initial and final electronic states are the same, this state needs to have
a permanent electric dipole moment. Thus we can have purely rotational
radiative transitions in heteronuclear diatomic molecules like HCl and CO,
which have permanent dipole moments, but not in homonuclear ones like
H2 and O2 .4
The usual electric dipole selection rules apply; ∆J = ±1, 0 with a parity
change. In a rotational state with angular momentum quantum numbers J
and mJ , the nuclear wavefunction φ({rN }) is proportional to the spherical
harmonic YJmJ , which has parity (−1)J . (For simplicity, we consider only
molecular states in which the electronic wavefunction has zero angular mo-
mentum and even parity, such as the diatomic 1 Σg states.) Then the fact
4
However, we can produce purely rotational transitions in all types of molecules by the
process of Raman scattering, in which a photon is effectively absorbed and then reemitted
by a molecule, since the virtual intermediate state can have a dipole moment.

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10.4. MOLECULAR SPECTRA 125

that the parity must change in a radiative transition excludes the possibil-
ity ∆J = 0. Therefore the possible energy changes in emission (J + 1 → J;
J = 0, 1, 2 · · ·) are given by:

!2 !2
∆E = [(J + 1)(J + 2) − J(J + 1)] = (J + 1) .
2I I
In fact, the rate for spontaneous emission between rotational states is very
small, because of the small energy release (varying as ω 3 ), and so rotational
transitions are more conveniently studied by absorption spectroscopy. The
same formula for the energies of transition clearly applies to the J → (J + 1)
absorption case. Therefore the spectrum is expected to consist of equally
spaced lines, separated by energy !2 /I. Observation of this spacing can be
used to determine the moment of inertia and hence the bond length of the
molecule. Strictly speaking the spacing isn’t quite uniform, because the radial
Schrödinger equation acquires a centrifugal potential term !2 J(J + 1)/2µR2
which means that the equilibrium separation slightly increases with J and
consequently the moment of inertia increases and the line spacing decreases.

& Exercise. Use perturbation theory to estimate the strength of the effect of
the centrifugal term.

& Info. The intensities of rotational spectral lines show some interesting
features. Although the transition matrix element depends on the quantum numbers,
the dominant factor is usually the population of the initial state. As mentioned
earlier, non-radiative transitions due to molecular collisions bring about a thermal
distribution,

nJ ∝ gJ exp[−EJ /kB T ] ∝ (2J + 1) exp[−!2 J(J + 1)/2IkB T ] .

This increases with J up to some value, which depends on the temperature, and then
decreases. Thus successive spectral lines increase and then decrease in intensity.

10.4.2 Vibrational transitions

Another important type of molecular motion is vibration, in which the nuclei
oscillate around their equilibrium positions. For a diatomic molecule, we can
Taylor expand the molecular potential E0 (R) around the equilibrium nuclear
separation R0 to obtain
1
E0 (R) = E0 (R0 ) + (R − R0 )2 ∂R
2
E0 |R0 + . . . .
2
Keeping only the two terms shown on the right-hand side, we have the poten-
tial for a simple harmonic oscillator with classical frequency ω = ((1/µ)∂R
2 E | )1/2
0 R0
where µ is the reduced mass. Thus we expect the energy levels including nu-
clear vibration to be given by

E = E0 (R0 ) + (n + 1/2)!ω, n = 0, 1, 2, . . . .

The excitation energies of molecular vibrational (states are typically larger

than those of rotational states by a factor of about ( mN /me and smaller than
electronic excitation energies by a factor of about me /mN . As we discussed
earlier, E0 (R0 ) will be of the same order of magnitude as atomic energies, i.e.
of the order of !2 /me a20 where a0 is the Bohr radius. Thus, on dimensional

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10.4. MOLECULAR SPECTRA 126

grounds, ∂R 2 √
0 R0 will be of order ! /me a0 , and !ω ∼ ! / me mN a0 . There-
2E | 2 4 2

fore
( the vibrational energy is smaller than the electronic by a factor of order
me /mN . This puts vibrational spectra in the wavelength region around
10µm, which is in the infra-red.
We can now check explicitly that the Born-Oppenheimer approximation
is valid for nuclear vibrational states, as follows.
( The mean square nuclear
vibrational momentum
( is of order mN !ω ∼ mN /me (!/a0 )2 , which means
that ∇N φk ∼ mN /me φk /a20 , where φk is the nuclear part of the wavefunc-
2

tion. On the other hand ∇2N ψk ∼ ψk /a20 , where ψ(k is the electronic part. Thus
φk ∇2N ψk is smaller than ψk ∇2N φk by a factor of me /mN , and it is legitimate
to neglect the former.
For vibrational transitions we have the selection rule (exercise)

∆n = ±1 .

This implies only a single energy in the spectrum,

∆E = (En+1 − En ) = !ω ,

corresponding to the classical frequency of oscillation. In practice the Taylor

expansion around R = R0 has non-negligible terms of higher than second or-
der and the harmonic oscillator approximation is not very reliable: there is Figure 10.2: Generally vibra-
anharmonicity. The flattening of the molecular potential energy curve at tional transitions occur in con-
larger separations has the effect of bringing the energy levels closer together. junction with rotational transi-
tions. Consequently, it is pos-
Thus transitions at larger n have lower energies than that given above. Also,
sible to observe both rotational
since the true stationary state wavefunctions are not precisely harmonic os- and vibrational transitions in the
cillator eigenfunctions, our selection rule is not exactly valid, and transitions vibrational spectrum. The top
with |∆n| > 1 become possible. figure shows an energy level dia-
gram demonstrating some of the
& Info. Vibrational modes for polyatomic molecules can be quite com- transitions involved in the IR
plicated. If there are N atoms, in general there are 3N − 6 normal modes (3N vibration-rotation spectrum of a
linear molecule: P branch (where
coordinates, less 3 to define the overall position of the centre of mass, and less 3 to
∆J = 1), Q branch (not always
define the overall orientation of the molecule) or 3N − 5 in the case of a diatomic allowed, ∆J = 0) and R branch
molecule. Thus, in the simple case of the linear CO2 molecule, there are four modes, (∆J = +1). The lower fig-
two with the atoms remaining collinear (one with the two O atoms moving in an- ure shows the vibration-rotation
tiphase with the C stationary, and one with the O atoms moving in phase in the spectrum of HCl. The left hand
opposite direction to the C atom) and two degenerate orthogonal bending modes. branch of the spectrum repre-
In the following chapter, we will turn to consider the vibrational motion of periodic sents the P branch and the right
the R. The Q branch is not al-
lattice systems where, once again, a degree of simplicity is restored!
lowed. The splitting of the lines
is associated with the two iso-
topes 35 Cl and 37 Cl.

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Chapter 11

Field theory: from phonons

to photons

In our survey of single- and “few”-particle quantum mechanics, it has been

possible to work with a discrete representation in which we index individual
constituent particles. However, when the “elementary excitations” of the sys-
tem involve the coherent collective motion of many individual discrete particle
degrees of freedom – such as the wave-like atomic vibrations of an ordered
elastic solid, or where discrete underlying classical particles can not even be
identified – such as the electromagnetic field, such a representation is incon-
venient or even inaccessible. In such cases, it is useful to turn to a continuum
formulation of quantum mechanics. In the following, we will develop these
fundamental ideas on the background of the simplest continuum theory: lat-
tice vibrations of the atomic chain. As we will see, this study will provide
a platform to investigate the quantum mechanics of the electromagnetic field
– the subject of quantum electrodynamics – and will pave the way to the
development of quantum field theory of relativistic particles.

11.1 Quantization of the classical atomic chain

As a simplified model of an ordered (one-dimensional) crystal, let us consider
a chain of point particles each of mass m (atoms) which are elastically con-
nected by springs with spring constant ks (chemical bonds) (see Fig. 11.1).
Although our target will be to construct a quantum theory of the elementary
vibrational excitations, it is helpful to begin our analysis by reviewing the
classical properties of the system.

11.1.1 Classical chain

For reasons that will become clear, it is instructive to consider the Lagrangian
formulation of the problem. For the N -atom chain, the classical Lagrangian
is given by,
N "
! #
m ks
L=T −V = ẋ2n − (xn+1 − xn − a) ,
2
(11.1)
2 2
n=1

where the first term accounts for the kinetic energy of the particles whilst the
second describes their coupling.1 For convenience, we adopt periodic boundary
1
In real solids, the inter-atomic potential is, of course, more complex than our quadratic
approximation. Yet, for “weak coupling”, the harmonic contribution dominantes (cf. our
discussion of molecular vibrations). For the sake of simplicity we, therefore, neglect the
effects caused by higher order contributions.

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 128

Figure 11.1: Toy model of a one-dimensional solid: a chain of point-like particles

each of mass m coupled elastically by springs with spring constant ks .

conditions such that xN +1 ≡ N a + x1 where a denotes the “natural” equilib-

rium lattice spacing. Anticipating that the effect of lattice vibrations on the
solid is weak (i.e. long-range atomic order is maintained) we will assume that
(a) the n-th atom has its equilibrium position at x̄n ≡ na, and (b) that the
deviation from the equilibrium position remains small (|xn (t) − x̄n | # a), i.e. Joseph-Louis Lagrange 1736-
the integrity of the solid is maintained. With xn (t) = x̄n + φn (t) (φN +1 = φ1 ) 1813:
the Lagrangian (11.1) then takes the form A mathematician
who excelled
N "
! # in all fields
m ks 2 of analysis,
L= φ̇2n − (φn+1 − φn ) . number theory,
2 2 and celestial
n=1
mechanics. In
Now, typically, we are not concerned with the behaviour of a given system 1788 he pub-
lished Mécanique
on ‘atomic’ length scales. (For such purposes, our model is in any case much Analytique, which summarised all
to primitive!) Rather, we are interested in universal features, i.e. experimen- of the work done in the field of
mechanics since the time of Newton,
tally observable behaviour, common to a wide range of physical systems, that and is notable for its use of the
manifests itself on macroscopic length scales where the detailed form of the theory of differential equations. In
it he transformed mechanics into a
model is inessential. For example, we might wish to study the specific heat of branch of mathematical analysis.
the solid in the limit of infinitely many atoms (or at least a macroscopically
large number, O(1023 )). Under these conditions, microscopic models can usu-
ally be substantially simplified. In particular it is often permissible to subject
a discrete lattice model to a continuum approximation, i.e. to neglect the
discreteness of the microscopic entities of the system and to describe it in
terms of effective continuum degrees of freedom. In the present case, taking a
continuum limit amounts to describing the lattice displacements φn in terms
of smooth functions, φ(x) of a continuous variable x (see figure). Clearly such
a description makes sense only if relative fluctuations on atomic scales are
weak (for otherwise the smoothness condition would be violated).

" Exercise. Starting with the discrete form of the Lagrangian, or otherwise,
show the classical equations of motion take the form,

mφ̈n = ks a2 (φn+1 − 2φn + φn−1 ) .

Remembering that the boundary conditions are periodic, obtain the normal modes. Hint: consider the ansatz,
From this result, determine the condition under which the continuum approximation φn (t) = ei(kna−ωt) .
can be justified.

Introducing continuum degrees of freedom, φ(x), and applying a first order

Taylor expansion,2 we can define
$ $ N %
$ $ ! 1 L
φn → φ(x)$$ , φn+1 − φn → a∂x φ(x)$$ , → dx,
x=na x=na a 0
n=1
2
Indeed, for reasons that will become clear, higher order contributions to the Taylor
expansion do not contribute to the low-energy properties of the system where the continuum
approximation is valid.

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 129

where L = N a (not to be confused with the Lagrangian itself!) denotes the

total length of the chain. Expressed in terms of the new&degrees of freedom,
L
the continuum limit of the Lagrangian then reads L[φ] = 0 dx L(φ̇, φ), where

ρ 2 κs a2
L(φ̇, φ) = φ̇ − (∂x φ)2 , (11.2)
2 2
denotes the Lagrangian density, ρ = m/a denotes the mass per unit length
and κs = ks /a. The corresponding classical action is given by
%
S[φ] = dt L[φ] . (11.3)

Thus, we have succeeded in trading the N -point particle description in

for one involving continuous degrees of freedom, φ(x), a (classical) field.
The dynamics of the latter are specified by “functionals” L[φ] and S[φ] which
represent the continuum generalizations of the discrete classical Lagrangian
and action, respectively.3 However, although we have achieved a continuum
formulation, we have yet to extract concrete physical information from the Sir William Rowan Hamilton
action. To do so, we need to derive equations of motion. At first sight, it may 1805-1865:
A mathematician
not be entirely clear what is meant by ‘equations of motion’ in the context of credited with
an infinite dimensional model. The answer to this question lies in Hamilton’s the discovery
extremal principle of classical mechanics: of quaternions,
the first non-
commutative
" Info. Hamilton’s extremal principle: Suppose that the dynamics of a algebra to be
classical point particle with& coordinate x(t) is described by the classical Lagrangian studied. He also
invented impor-
L(x, ẋ), and action S[x] = dtL(x, ẋ). Hamilton’s extremal principle states that the tant new methods in Mechanics.
configurations x(t) that are actually realized are those that extremize the action. This
means that, for any smooth curve y(t),
1
lim (S[x + &y] − S[x]) = 0 , (11.4)
"→0&
i.e. to first order in &, the action has to remain invariant. Applying this condition,
one finds that it is fulfilled if and only if x(t) obeys the Euler-Lagrange equation
of motion (exercise),

d
(∂ẋ L) − ∂x L = 0 . (11.5)
dt

Now, in Eq. (11.3), we are dealing with a system of infinitely many degrees
of freedom, φ(x, t). Yet Hamilton’s principle is general, and we may see what
happens if (11.3) is subjected to an extremal principle analogous to Eq. (11.4).
To do so, we must effect the substitution φ(x, t) → φ(x, t) + &η(x, t) into
Eq. (11.3) and demand that the contribution first order in & vanishes. When
applied to the specific Lagrangian (11.2), a substitution of the of the ‘varied’
field leads to
% % L ' (
S[φ + &η] = S[φ] + & dt dx ρ φ̇η̇ − κs a2 ∂x φ∂x η + O(&2 ).
0

Integrating by parts (with respect to time for the first term under the inte-
gral, and space in the second) and demanding that the contribution linear
3
In the mathematics and physics literature, mappings of functions into the real or com-
plex numbers are generally called functionals. The argument of a functional is commonly
indicated in rectangular brackets [ · ]. For example, in this case, S maps the ‘functions’
∂x φ(x, t) and φ̇(x, t) to the real number S[φ].

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 130

& &L
in & vanishes, one obtains dt 0 dx(ρφ̈ − κs a2 ∂x2 φ)η = 0. (Notice that the
boundary terms associated with both t and x vanish identically.4 Now, since η
was defined to be any arbitrary smooth function, the integral above can only
vanish if the term in parentheses is globally vanishing. Thus the equation of
motion takes the form of a wave equation,

ρφ̈ = κs a2 ∂x2 φ . (11.6)

The solutions
) of Eq. (11.6) have the general form φ+ (x + vt) + φ− (x − vt)
where v = a κs /ρ, and φ± are arbitrary smooth functions of their argument.
From this we can deduce that the basic low energy elementary excitations
of our model are lattice vibrations propagating as sound waves to the left or
right at a constant velocity v (see figure). The trivial behaviour of our model
is of course a direct consequence of its simplistic definition — no dissipation,
dispersion or other non-trivial ingredients. Adding these refinements leads to
the general classical theory of lattice vibrations. With this background, let us
now turn to the consider the quantization of the quantum mechanical chain.

11.1.2 Quantum chain

In addressing the quantum description, the first question to ask is a con-
ceptual one: is there a general methodology to quantize models of the form
described by the atomic chain (11.2)? Indeed, there is a standard procedure
to quantize continuum theories which closely resembles the quantization of
point mechanics. The first step is to introduce canonical momenta conjugate
to the continuum degrees of freedom (coordinates), φ, which will later be used
to introduce canonical commutation relations. The natural generalization of
the definition pn ≡ ∂ẋn L of point mechanics to a continuum suggests setting

π = ∂φ̇ L(φ̇, φ) . (11.7)

In common with φ(x, t), the canonical momentum, π(x, t), is a continuum
degree of freedom. At each space point it may take an independent& value.
From the Lagrangian, we can define the Hamiltonian, H[φ, π] ≡ dx H(φ, π),
where H(φ, π) ≡ π φ̇−L(φ̇, φ). represents the Hamiltonian density. Applied
to the atomic chain (11.2), the canonical momentum π = ρφ̇ and H(φ, π) =
π2 κs a2
2ρ + 2 (∂x φ) .
2

In this form, the Hamiltonian can be quantized according to the following

rules: (a) promote the fields φ(x) and π(x) to operators: φ %→ φ̂, π %→ π̂, and
(b) generalise the canonical commutation relations of one-particle quantum
mechanics, [p̂m , xn ] = −i!δmn , according to the relation5

[π̂(x), φ̂(x" )] = −i!δ(x − x" ) . (11.8)

Operator-valued functions like φ̂ and π̂ are generally referred to as quantum

fields. Employing these definitions, we obtain the quantum Hamiltonian den-
sity

1 2 κs a2
Ĥ(φ̂, π̂) = π̂ + (∂x φ̂)2 .
2ρ 2
4
If we assume that the function φ already obeys the boundary conditions, we must have
η(0, t) = η(L, t) = η(x, 0) = η(x, T ) = 0).
5
Note that the dimensionality of both the quantum and classical continuum fields is
compatible with the dimensionality of the Dirac δ-function, [δ(x − x! )] = [Length]−1 .

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 131

" Exercise. To develop this field theoretical formulation of the Hamiltonian, we

have pursued a Lagrangian formulation. If you feel uncertain about this methodology,
you should explore the derivation of Ĥ directly from the discrete atomic formulation.
First, show that, for the discrete harmonic chain, the classical Hamiltonian is given
by
! " p2 ks
#
Ĥ = n
+ (φn+1 − φn )2 .
n
2m 2

Promoting the displacements and momenta to operators, and applying the canonical
quanitization conditions, [p̂n , φn! ] = −i!δnn! , obtain the discrete form of the Hamilto-
nian. Taking the continuum limit, show that the Hamiltonian recovers the continuum
form derived through the Lagrangian formulation.

The Hamiltonian represents a quantum field theoretical formulation of the

problem but not yet a solution. To address the quantum properties of the
system, it is helpful now to switch to a Fourier representation. As with any
function, operator-valued functions can be represented in a variety of different
ways. In particular they can be subjected to Fourier expansion,
* % L * * *
φ̂k ≡ 1 {∓ikx φ̂(x) φ̂(x) 1 ! {±ikx φ̂k
dx e , = e ,(11.9)
π̂k L1/2 0 π̂(x) π̂(x) L1/2 k π̂k
+
where k represents the sum over all Fourier coefficients indexed by quantized
wavevectors k = 2πm/L, m integer. Note that, since the classical field φ(x)
is real, the quantum field φ̂(x) is Hermitian, i.e. φ̂k = φ̂†−k (and similarly for
π̂k ). In the Fourier representation, the transformed field operators obey the
canonical commutation relations (exercise),

[π̂k , φ̂k! ] = −i!δkk! .

" Exercise. Making use of Eqs. (11.8) and (11.9) derive the canonical commu-
tation relation above.

When expressed in the Fourier representation, making use of the identity

δk+k! ,0
% , % -. /
L ! 1 L
!
!
dx (∂ φ̂)2 = (ik φ̂k )(ik " φ̂k! ) dx ei(k+k )x = k 2 φ̂k φ̂−k ,
0 !
L 0
k,k k

&L
together with the parallel relation for 0 dx π̂ 2 , the Hamiltonian assumes the
“near diagonal” form,
!" 1 1 2
#
Ĥ = π̂k π̂−k + ρωk φ̂k φ̂−k , (11.10)
2ρ 2
k

where ωk = v|k|, and v = a(κs /ρ)1/2 denotes the classical sound wave ve-
locity. In this form, the Hamiltonian can be identified as nothing more than
a superposition of independent quantum harmonic oscillators. The only dif-
ference between (11.10) and the canonical form of an oscillator Hamiltonian
p2
H = 2m + 12 mω 2 x2 is the presence of sub-indices k and −k (a consequence
†
of φ̂k = φ̂−k ). As we will show shortly, this difference is inessential. This

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 132

result is actually not difficult to understand (see figure): Classically, the sys-
tem supports a discrete set of wave-like excitations, each indexed by a wave
number k = 2πm/L. Within the quantum picture, each of these excitations is
described by an oscillator Hamiltonian with a k-dependent frequency. How-
ever, it is important not to confuse the atomic constituents, also oscillators
(albethey coupled), with the independent collective oscillator modes described
by Ĥ.
The description above, albeit perfectly valid, still suffers from a deficiency:
Our analysis amounts to explicitly describing the effective low energy excita-
tions of the system (the waves) in terms of their microscopic constituents (the
atoms). Indeed the different contributions to Ĥ keeps track of details of the
microscopic oscillator dynamics of individual k-modes. However, it would be
much more desirable to develop a picture where the relevant excitations of the
system, the waves, appear as fundamental units, without explicit account of
underlying microscopic details. (As with hydrodynamics, information is en-
coded in terms of collective density variables rather than through individual
molecules.) To understand how this programme can be achieved let us recall
the properties of the quantum harmonic oscillator.

" Info. In quantum mechanics, the harmonic oscillator has the status of a
single-particle problem. However, the fact that the energy levels, &n = !ω(n + 1/2),
are equidistant suggests an alternative interpretation: One can think of a given energy
state &n as an accumulation of n elementary entities, or quasi-particles, each having
energy !ω. What can be said about the features of these new objects? First, they
are structureless, i.e. the only ‘quantum number’ identifying the quasi-particles is
their energy !ω (otherwise n-particle states formed of the quasi-particles would not
be equidistant). This implies that the quasi-particles must be bosons. (The same
state !ω can be occupied by more than one particle — see figure.) This idea can be
formulated in quantitative terms by employing the formalism of ladder operators in
which )the operators p̂ and )
x̂ are traded for the pair of Hermitian adjoint operators
a ≡ mω 2! (x̂ + mω
i
p̂), a†
≡ 2! (x̂ − mω p̂). Up to a factor of i, the transformation
mω i

(x̂, p̂) → (a, a† ) is canonical, i.e. the new operators obey the canonical commutation
relation, [a, a† ] = 1. More importantly, in the a-representation, the Hamiltonian
takes the simple form, Ĥ = !ω(a† a + 1/2), as can be checked by direct substitution.
The complete hierarchy of higher energy states can be generated by setting |n& ≡
√1 (a† )n |0&.
n!
While the a-representation provides another way of constructing eigenstates of
the quantum harmonic oscillator, its real advantage is that it naturally affords a
many-particle interpretation. Temporarily forgetting about the original definition of
the oscillator, we can declare |0& to be a ‘vacuum’ state, i.e. a state with no particles
present. a† |0& then represents a state with a single featureless particle (the operator
a† does not carry any quantum number labels) of energy !ω. Similarly, (a† )n |0& is
considered as a many-body state with n particles, i.e. within the new picture, a† is
an operator that creates particles. The total energy of these states is given by !ω ×
(occupation number). Indeed, it is straightforward to verify that a† a|n& = n|n&, i.e.
the Hamiltonian basically counts the number of particles. While, at first sight, this
may look unfamiliar, the new interpretation is internally consistent. Moreover, it
fulfils our objective: it allows an interpretation of the excited states of the harmonic
oscillator as a superposition of independent structureless entities.

With this background, we may return to the harmonic atomic chain (11.10)

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11.1. QUANTIZATION OF THE CLASSICAL ATOMIC CHAIN 133

and, inspired by the ladder operator formalism, define6

0 1 2 0 1 2
mωk i † mωk i
ak ≡ φ̂k + π̂−k , ak ≡ φ̂−k − π̂k .
2! mωk 2! mωk
With this definition, one finds that the ladder operators obey the commutation
relations (exercise)

[ak , a†k! ] = δkk! , [ak , ak! ] = [a†k , a†k! ] = 0 , (11.11)

and the Hamiltonian assumes the diagonal form

! 1 2
† 1
Ĥ = !ωk ak ak + . (11.12)
2
k

Eqs. (11.11) and (11.12) represent the final result of our analysis: The low-lying
elementary excitations of the discrete atomic chain are described by oscillator
Figure shows a typical measured
wave-like modes – known as phonons – each characterised by a wavevector k phonon dispersion of an ordered
and a linear dispersion, ωk = v|k|. A generic state of the system is given by crystalline solid obtained by neu-
1 tron scattering. The x-axis in-
|{nk } = (n1 , n2 , · · ·)& = )3 (a†k1 )n1 (a†k2 )n2 · · · |0& . dexes wavenumbers along a lat-
i ni ! tice direction (specified in units
of π/a). Three generic aspects
The representation derived above illustrates the capacity to think about
are visible: (1) near k = 0, the
quantum problems in different complementary “pictures”, a principle that dispersion is, as expected, linear.
finds innumerable applications. The existence of different interpretations of a (2) The several branches are as-
given system is by no means heretic but, rather, is consistent with the spirit sociated with different “polariza-
of quantum mechanics. Indeed, it is one of the prime principles of quan- tions” of the lattice fluctuations.
tum theories that there is no such thing as ‘the real system’ which underpins (3) For wavelengths comparable
the phenomenology. The only thing that matters is observable phenomena. to the lattice spacing, k ∼ π/a,
non-universal features specific to
For example, the ‘fictitious’ quasi-particle states of the harmonic chain, the
the particular material become
phonons, behave as ‘real’ particles, i.e. they have dynamics, can interact, be visible.
detected experimentally, etc. From a quantum point of view there is actually
no fundamental difference between these objects and ‘real’ particles.

" Example: Debye theory of solids: Our analysis above focussed on the
longitudinal vibrations of the one-dimensional atomic chain. In three-dimensions,
each mode is associated with three possible polarizations, λ: two transverse and one
longitudinal. Taking into account all degrees of freedom, it is straightforward to show
Peter Josephus Wilhelmus De-
that the generalized Hamiltonian takes the form, bye 1884-1966:
! 1 2 Dutch-American
† 1
Ĥ = !ωk ak,λ ak,λ + , physicist
2 renowned for his
kλ
work on molec-
ular structure,
where, for simplicity, we assume that the dispersion, ωk = v|k| is independent of
especially dipole
polarization. Let us use this result to obtain the internal energy and specific heat moments and
due to phonons. Now, for an equilibrium thermal distribution, the average phonon the diffraction
occupancy of state (k, λ) is given simply by the Bose-Einstein distribution, nB (!ωk ) ≡ of X-rays and
electrons in
1
e!ωk /kB T −1
. The internal energy is therefore given by gases. Debye was awarded a Nobel
! ! " # Prize in Chemistry, 1936, “for his
1 1 contributions to our knowledge of
E= !ωk (nB (!ωk ) + 1/2) = !ωk + .
kλ kλ
e!ωk /kB T − 1 2 molecular structure through his
investigations on dipole moments
and on the diffraction of X-rays and
In the thermodynamic limit, where N ≡ V /a3 → ∞, we may replace the sum over electrons in gases”.
+ & kD d3 k & kD 2
modes by an integral, k → V 0 (2π)3 = 2π 2 0 k dk, where kD , denotes the
V

6
As for the consistency of these definitions, recall that φ̂†k = φ̂−k and π̂k† = π̂−k . Under
these conditions the second of the definitions below indeed follows from the first upon taking
the Hermitian conjuate.

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11.2. QUANTUM ELECTRODYNAMICS 134

largest wave vector accessible in the crystal. We can fix kD by ensuring that the
total number of modes (for each polarization) matches the total number of degrees
2 1/3
of freedom, i.e. (2π)13 /V 43 πkD
3
= N , i.e. kD = (6π a) . The corresponding frequency
scale, ωD = vkD , is known as the Debye frequency. In this limit, dropping the tem-
perature independent contribution from zero point fluctuations, the internal energy
per particle is given by
%
E 3a3 kD 2 !vk
ε≡ = k dk !vk/k T .
N 2π 2 0 e B −1
& T /T z 3 dz
Then, defining the Debye temperature, TD = !vkD /kB , we have ε = 9kB T ( TTD )3 0 D ez −1 .
The corresponding specific heat per particle can be obtained from the temperature
derivative and leads to
1 23 % TD /T
T z 4 dz
cV = 9kB .
TD 0 (ez − 1)2
In particular, at high temperatures, we recover the Dulong-Petit law, cV = 3kB
following from the equipartition theorem – each degree of freedom is associated with
an energy kB T /2. At low temperatures, T # TD , we may replace the upper limit on
the integral by ∞ from which we find that cV ∼ T 3 . Both limits compare well with
experiment (see figure).

This completes our discussion of the classical and quantum field theory of
the harmonic atomic chain. In this example, we have seen how we can effect a
quantum formulation of a continuum system. Using the insights obtained in
this example, we now turn to consider the quantization of the electromagnetic
field.

11.2 Quantum electrodynamics

In common with the continuous formulation of the atomic chain, in vacua,
the electromagnetic (EM) field satisfies a wave equation. The generality of
the procedure outlined above suggests that the quantization of the EM field
might therefore proceed in an entirely analogous manner. However, there are
a number of practical differences that make quantization a slightly more diffi-
cult enterprise: Firstly, the vector character of the vector potential A, along-
side relativistic covariance, gives the problem a non-trivial internal geometry.
Moreover, the gauge freedom of the vector potential introduces redundant de-
grees of freedom whose removal on the quantum level is not straightforward.
To circumvent a lengthy discussion of these issues, we will not address the
problem of EM field quantization in all its detail.7 On the other hand, the
photon field plays a much too important role in all branches of physics for us to
drop the problem altogether. We will therefore aim at an intermediate exposi-
tion, largely insensitive to the problems outlined above but sufficiently general
to illustrate the main principles. As with the harmonic chain, to prepare the
way, we begin by developing the classical field theory of the EM field.

11.2.1 Classical theory of the electromagnetic field

In vacuum, the Lagrangian density of the EM field is given by L = − 4µ1 0 Fµν F µν
(summation convention implied) where µ0 = 4π ×10−7 Hm−1 denotes the vac-
7
Readers interested in a more thorough and illuminating exposition are referred to the
literature, e.g., L. H. Ryder, Quantum Field Theory (Cambridge University Press, 1996),
or the excellent lecture notes of Eduardo Fradkin that have been made available online at
http://webusers.physics.illinois.edu/ efradkin/phys582/physics582.html.

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11.2. QUANTUM ELECTRODYNAMICS 135

uum permeability,
 
0 −Ex /c −Ey /c −Ez /c
 Ex /c 0 Bz −By 
Fµν = ∂µ Aν − ∂ν Aµ = 
 Ey /c

−Bz 0 Bx 
Ez /c By −Bx 0 µν

denotes the EM field tensor, E = Ȧ is the electric field, and B = ∇ × A is the

magnetic field. As a first step towards quantization, we must specify a gauge.
In the absence of charge, a particularly convenient choice is the Coulomb
gauge, ∇ · A = 0, with the scalar component φ = 0.8 Using these gauge
conditions, one may verify that the classical Lagrangian assumes the form,
% " #
1 1 2
L[A(x, t)] = d3 x Ȧ − (∇ × A)2
. (11.13)
2µ0 c2

The corresponding classical Euler-Lagrange equations of motion, ∂µ F µν = 0,

translate to the wave equation (exercise)

1
Ä = ∇2 A .
c2
The structural similarity between the EM field and the continuous formu-
lation of the harmonic chain is clear. By analogy with our discussion above,
we should now switch to the Fourier representation and quantize the classical
field. However, in contrast to our analysis of the chain, we are now dealing (i)
with the full three-dimensional Laplacian acting upon (ii) the vector field A
that is (iii) subject to the constraint ∇ · A = 0. It is these aspects which lead
to the complications outlined above.
We can circumvent these difficulties by considering cases where the geom-
etry of the system reduces the complexity of the eigenvalue problem while still
retaining the key conceptual aspects of the problem. This restriction is less
artificial than it might appear. For example, just as the field φ in the classical
atomic chain can be expanded in Fourier harmonics, in long waveguides, the
EM vector potential can be expanded in solutions of the eigenvalue equation9

−∇2 uk (x) = λk uk (x), (11.14)

where k denotes a discrete one-dimensional

& index, and the vector-valued func-
tions uk are real and orthonormalized, d3 x uk · uk! = δkk! . The dependence
of the eigenvalues λk on k depends on details of the geometry and need not
be specified for the moment.

" Info. An electrodynamic waveguide is a quasi one-dimensional cavity with

metallic boundaries (see Fig. 11.2). The practical advantage of waveguides is that
they are good at confining EM waves. At large frequencies, where the wavelengths
are of order meters or less, radiation loss in conventional conductors is high. In these
frequency domains, hollow conductors provide the only practical way of transmit-
ting radiation. EM field propagation inside a waveguide is constrained by boundary
conditions. Assuming the walls of the system to be perfectly conducting,

E$ (xb ) = 0, B⊥ (xb ) = 0 , (11.15)

8
Keep in mind that, once a gauge has been set, we cannot expect further results to display
“gauge invariance.”
9
More precisely, one should say that Eq. (11.14) defines the set of eigenfunctions relevant
for the low-energy dynamics of the waveguide. More complex eigenfunctions of the Laplace
operator exist but they involve much higher energy.

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11.2. QUANTUM ELECTRODYNAMICS 136

Figure 11.2: EM waveguide with rectangular cross-section. The structure of the

eigenmodes of the EM field is determined by boundary conditions at the walls of the
cavity.

where xb parameterize points on the boundary of the system, and E$ (B⊥ ) is the
parallel (perpendicular) component of the electric (magnetic) field. Applied to the
problem at hand, let us consider a long cavity with uniform rectangular cross-section
Ly × Lz . To conveniently represent the Lagrangian of the system, we wish to express
the vector potential in terms of eigenfunctions uk that are consistent with the bound-
ary conditions (11.15). A complete set of functions fulfilling this condition is given
by
 
c1 cos(kx x) sin(ky y) sin(kz z)
uk = Nk  c2 sin(kx x) cos(ky y) sin(kz z)  .
c3 sin(kx x) sin(ky y) cos(kz z)

Here ki = ni π/Li , with i = x, y, z and ni is integer, Nk is a factor normalizing uk to

unit modulus, and the coefficients ci are subject to the condition c1 kx + c2 ky + c3 kz =
0 (reflecting the gauge choice ∇ · A = 0). Indeed, + it is straightforward to verify
that a general superposition of the type A(x, t) ≡ k αk (t)uk (x), αk (t) ∈ R, is
divergenceless, and generates an EM field compatible with (11.15). Substitution of
uk into (11.14) identifies the eigenvalues as λk = kx2 + ky2 + kz2 .
In the physics and electronic engineering literature, eigenfunctions of the Laplace
operator in a quasi-one-dimensional geometry are commonly described as modes.
As we will see shortly, the energy of a mode (i.e. the Hamiltonian evaluated on a
specific mode configuration) grows with λk . In cases where one is interested in the
low-energy dynamics of the EM field, only configurations with small λk are relevant.
For example, let us consider a massively anisotropic waveguide with Lz < Ly # Lx .
In this case the modes with smallest λk are those with kz = 0, ky = π/Ly , and
kx ≡ k # L−1 z,y . With this choice,

1 22
2 π
uk = √ sin(πy/Ly ) sin(kx) êz , λk = k +
2
, (11.16)
V Ly

and a scalar index k suffices to label both eigenvalues and eigenfunctions uk . A

caricature of the spatial structure of the functions uk is shown in Fig. 11.2.

Returning to the problem posed by (11.13) and (11.14), one + can expand
the vector potential in terms of eigenfunctions uk as A(x, t) = k αk (t)uk (x),
where the sum runs over all allowed values of the index parameter k. (In a
waveguide of length L, k = πn/L with n integer.) Substituting this expan-
sion into (11.13), and using the normalization properties of uk , we obtain the
Lagrangian,
" #
1 ! 1 2
L[α̇, α] = α̇ − λ 2
k k ,
α
2µ0 c2 k
k

i.e. a decoupled representation where the system is described in terms of

independent dynamical systems with coordinates αk . From this point on, the
quantization procedure mirrors that of the atomic chain.

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11.2. QUANTUM ELECTRODYNAMICS 137

11.2.2 Quantum field theory of the electromagnetic field

To achieve the electromagnetic field quantization, we first define the canonical
momenta through the relation,
πk = ∂α̇k L = &0 α̇k ,
where &0 = 1/µ0 c2 denotes+the vacuum permittivity, which leads to the
classical Hamiltonian H = k ( 2'10 πk2 + 12 &0 c2 λk αk2 ). Next we quantize the the-
ory by promoting fields to operators αk → α̂k and πk → π̂k , and declare the
canonical commutation relations [π̂k , α̂k! ] = −i!δkk! . The quantum Hamilto-
nian operator, again of harmonic oscillator type, then reads
! " π̂ 2 1
#
Ĥ = k
+ &0 ωk α̂k ,
2 2
2&0 2
k

where ωk2 = c2 λk .
Then, guided by the analysis of the atomic chain, we now introduce the
ladder operators,
0 1 2 0 1 2
&0 ωk i † &0 ωk i
ak = α̂k + π̂k , ak = α̂k − π̂k ,
2! &0 ωk 2! &0 ωk
whereupon the Hamiltonian assumes the now familiar form
! 1 2
† 1
Ĥ = !ωk ak ak + . (11.17)
2
k

For the specific problem of the first excited mode in a waveguide of width
Ly , !ωk = c[k 2 + (π/Ly )2 ]1/2 . Eq. (11.17) represents our final result for the
quantum Hamiltonian of the EM waveguide. Before concluding this section
let us make a few comments on the structure of the result.

" Firstly, notice that the construction above almost completely paralleled
our previous discussion of the atomic chain.10 The structural similarity
between the two systems finds its origin in the fact that the free field
Lagrangian (11.13) is quadratic in the fields and, therefore, bound to
map onto an oscillator-type Hamiltonian. That we obtained a simple
one-dimensional superposition of oscillators is due to the boundary con-
ditions specific to a narrow waveguide. For less restrictive geometries,
e.g. free space, a more complex superposition of vectorial degrees of free-
dom in three-dimensional space would have been obtained (see below).
However, the principal mapping of the free EM field onto a superposition
of oscillators is independent of geometry.
" Physically, the quantum excitations described by (11.17) are, of course,
the photons of the EM field. The unfamiliar appearance of the dis-
persion ωk is again a peculiarity of the waveguide. However, in the
limit of large longitudinal wave numbers k - L−1 y , the dispersion ap-
proaches ωk . c|k|, i.e. the familiar linear (relativistic) dispersion of
the photon field. Also notice that, due to the equality of the Hamilto-
nians (11.12) and (11.17), all that has been said about the behavior of
the phonon modes of the atomic chain carries over to the photon modes
of the waveguide.
10
Technically, the only difference is that, instead of index pairs (k, −k), all indices (k, k)
are equal and positive. This can be traced back to the fact that we have expanded in terms
of the real eigenfunctions of the closed waveguide instead of the complex eigenfunctions of
the periodic oscillator chain.

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11.2. QUANTUM ELECTRODYNAMICS 138

" As with their phonon analogue, the oscillators described by (11.17) ex-
hibit zero-point fluctuations. It is a fascinating aspect of quantum elec-
trodynamics that these oscillations, caused by quantization of the most
relativistic field, surface at various points of non-relativistic physics, e.g.
the attraction of two conducting plates in vacuum – the Casimir effect.

With the analysis of the waveguide complete, let us go back and consider
the quantitization of the full three-dimensional system. For the waveguide, we
have found
+ that the vector potential can be expanded in modes of the cavity as
= k α̂k uk where, rearranging the expressions for the ladder operators,
Â(x) :
! †
α̂k = 2'0 ωk (ak + ak ). More generally, in a fully three-dimensional cavity, one
may show that11
;
! ! < =
Â(x) = êkλ akλ eik·x + ê∗kλ a†kλ e−ik·x ,
2&0 ωk V
kλ=1,2

where V denotes the volume of the system, ωk = c|k|, and the two sets of
polarization vectors, êkλ , are in general complex and normalized to unity,
ê∗kλ · êkλ = 1. To ensure that the vector potential satifies the Coulomb gauge
condition, we require that êkλ · k = ê∗kλ · k = 0, i.e. the two polarization
vectors are orthogonal to the wave vector. Two real vectors, êkλ correspond
to two linear polarizations while, for circular polarization, the vectors are
complex. It is also convenient to assume that the two polarization vectors are
mutually orthogonal, êkλ · êkµ = δµν . The corresponding operators obey the
commutation relations,

[akλ , a†k! λ! ] = δk,k! δλλ! , [akλ , ak! λ! ] = 0 = [a†kλ , a†k! λ! ] .

With these definitions, the Hamiltonian then takes the familiar form
! < =
Ĥ = !ωk a†kλ akλ + 1/2 , (11.18)
kλ

while, defining the vacuum, |Ω&, the eigenstates involve photon number states,

> (a† )nkλ

|{nkλ }& ≡ | · · · , nkλ , · · ·& = √kλ |Ω& .
kλ
nkλ !

Finally, in practical applications (including our forthcoming study of radiative

transitions in atoms), it is convenient to transfer the time-dependence to the
operators by turning to the Heisenberg representation. In this representation,
the field operators obey the Heisenberg equations of motion (exercise),
i
ȧkλ = [Ĥ, akλ ] = −iωk akλ .
!
Integrating, we have akλ (t) = akλ (0)e−iωk t , which translates to the relation
;
! ! < =
Â(x, t) = êkλ akλ ei(k·x−ωk t) + ê∗kλ a†kλ e−i(k·x−ωk t) .
2&0 ωk V
kλ=1,2

11 P R
In the infinite system, the mode sum becomes replaced by an integral, k → V
(2π)3
d3 k.

Advanced Quantum Physics

Chapter 12

Time-dependent perturbation
theory

So far, we have focused largely on the quantum mechanics of systems in

which the Hamiltonian is time-independent. In such cases, the time depen-
dence of a wavepacket can be developed through the time-evolution operator,
Û = e−iĤt/! or, when cast in terms of the eigenstates of the Hamiltonian,
!
Ĥ|n! = En |n!, as |ψ(t)! = e−iĤt/!|ψ(0)! = n e−iEn t/!cn (0)|n!. Although
this framework provides access to any closed quantum mechanical system, it
does not describe interaction with an external environment such as that im-
posed by an external electromagnetic field. In such cases, it is more convenient
to describe the induced interactions of a small isolated system, Ĥ0 , through a
time-dependent interaction V (t). Examples include the problem of magnetic
resonance describing the interaction of a quantum mechanical spin with an
external time-dependent magnetic field, or the response of an atom to an ex-
ternal electromagnetic field. In the following, we will develop a formalism to
treat time-dependent perturbations.

12.1 Time-dependent potentials: general formalism

Consider then the Hamiltonian Ĥ = Ĥ0 + V (t), where all time-dependence
enters through the potential V (t). In the Schrödinger representation, the
dynamics of the system are specified by the time-dependent wavefunction,
|ψ(t)!S through the Schrödinger equation i!∂t |ψ(t)!S = Ĥ|ψ(t)!S . However,
in many cases, and in particular with the current application, it is convenient
to work in the Interaction representation,1 defined by

|ψ(t)!I = eiĤ0 t/!|ψ(t)!S

where |ψ(0)!I = |ψ(0)!S . With this definition, one may show that the wave-
function obeys the equation of motion (exercise)
i!∂t |ψ(t)!I = VI (t)|ψ(t)!I (12.1)

where VI (t)!= eiĤ0 t/!V e−iĤ0 t/!. Then, if we form the eigenfunction expansion,
|ψ(t)!I = n cn (t)|n!, and contract the equation of motion with a general
state, "n|, we obtain
"
i!ċm (t) = Vmn (t)eiωmn t cn (t) , (12.2)
n

1
Note how this definition differs from that of the Heisenberg representation, |ψ!H =
iĤt/!
e |ψ(t)!S in which all time-dependence is transferred into the operators.

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12.1. TIME-DEPENDENT POTENTIALS: GENERAL FORMALISM 140

where the matrix elements Vmn (t) = "m|V (t)|m!, and ωmn = (Em − En )/! =
−ωnm . To develop some intuition for the action of a time-dependent potential,
it is useful to consider first a periodically-driven two-level system where the
dynamical equations can be solved exactly.

$ Info. The two-level system plays a special place in the modern development
of quantum theory. In particular, it provides a platform to encode the simplest
quantum logic gate, the qubit. A classical computer has a memory made up of
bits, where each bit holds either a one or a zero. A quantum computer maintains a
sequence of qubits. A single qubit can hold a one, a zero, or, crucially, any quantum
superposition of these. Moreover, a pair of qubits can be in any quantum superposition
of four states, and three qubits in any superposition of eight. In general a quantum
computer with n qubits can be in an arbitrary superposition of up to 2n different
states simultaneously (this compares to a normal computer that can only be in one
of these 2n states at any one time). A quantum computer operates by manipulating
those qubits with a fixed sequence of quantum logic gates. The sequence of gates to
be applied is called a quantum algorithm.
An example of an implementation of qubits for a quantum computer could start
with the use of particles with two spin states: |↓! and |↑!, or |0! and |1!). In fact any
system possessing an observable quantity A which is conserved under time evolution
and such that A has at least two discrete and sufficiently spaced consecutive eigenval-
ues, is a suitable candidate for implementing a qubit. This is true because any such
system can be mapped onto an effective spin-1/2 system.

$ Example: Dynamics of a driven two-level system: Let us consider a

two-state system with
# $ # $
E1 0 0 δeiωt
Ĥ0 = , V (t) = .
0 E2 δe−iωt 0

Specifying the wavefunction by the two-component vector, c(t) = (c1 (t) c2 (t)), Eq. (12.2)
translates to the equation of motion (exercise)
# $
0 ei(ω−ω21 )t
i!∂t c = δ c(t) ,
e−i(ω−ω21 )t 0

where ω21 = (E2 − E1 )/!. With the initial condition c1 (0) = 1, and c2 (0) = 0, this
equation has the solution,

δ2
|c2 (t)|2 = sin2 Ωt, |c1 (t)|2 = 1 − |c2 (t)|2 ,
δ 2 + !2 (ω − ω21 )2 /4

where Ω = ((δ/!)2 +(ω −ω21 )2 /4)1/2 is known as the Rabi frequency. The solution,
which varies periodically in time, describes the transfer of probability from state 1 to
state 2 and back. The maximum probability of occupying state 2 is a Lorentzian with

γ2
|c2 (t)|2max = ,
γ 2 + !2 (ω − ω21 )2 /4
taking the value of unity at resonance, ω = ω21 .

$ Exercise. Derive the solution from the equations of motion for c(t). Hint:
eliminate c1 from the equations to obtain a second order differential equation for c2 .

$ Info. The dynamics of the driven two-level system finds practical application
in the Ammonia maser: The ammonia molecule NH3 has a pryramidal structure
with an orientation characterised by the position of the “lone-pair” of electrons sited

Advanced Quantum Physics

12.2. TIME-DEPENDENT PERTURBATION THEORY 141

on the nitrogen atom. At low temperature, the molecule can occupy two possible
states, |A! and |S!, involving symmetric (S) or an antisymmetric (A) atomic con-
figurations, separated by a small energy splitting, ∆E. (More precisely, along the
axis of three-fold rotational symmetry, the effective potential energy of the nitrogen
Charles Hard Townes 1915-
atom takes the form of a double-well. The tunneling of the nitrogen atom through the
(left)
double well leads to the symmetric and asymmetric combination of states.) In a time- is an American
dependent uniform electric field the molecules experience a potential V = −µd · E, Nobel prize-
where E = Eêz cos ωt, and µd denotes the electric dipole moment. Since µd is odd un- winning physicist
and educator.
der parity transformation, P µd P = −µd , and P |A! = −|A! and P |S! = |S!, the ma-
Townes is known
trix elements of the electric dipole moment are off-diagonal: "S|µd |S! = "A|µd |A! = 0 for his work on
and "S|µd |A! = "S|µd |A! = & 0. the theory and
If we start with all of the molecules in the symmetric ground state, we have application of the maser – microwave
amplification by stimulated emission
shown above that the action of an oscillating field for a particular time can can drive of radiation, on which he got the
a collection of molecules from their ground state into the antisymmetric first excited fundamental patent, and other work
in quantum electronics connected
state. The ammonia maser works by sending a stream of ammonia molecules, traveling with both maser and laser devices.
at known velocity, down a tube having an oscillating field for a definite length, so the He received the Nobel Prize in
Physics in 1964.
molecules emerging at the other end are all (or almost all, depending on the precision
of ingoing velocity, etc.) in the first excited state. Application of a small amount of
electromagnetic radiation of the same frequency to the outgoing molecules will cause
some to decay, generating intense radiation and therefore a much shorter period for
all to decay, emitting coherent radiation.

12.2 Time-dependent perturbation theory

We now turn to consider a generic time-dependent Hamiltonian for which an
analytical solution is unavailable – sadly the typical situation! In this case,
we must turn to a perturbative analysis, looking for an expansion of the basis
coefficients cn (t) in powers of the interaction,

cn (t) = c(0)
n + cn (t) + cn (t) + · · · ,
(1) (2)

(m) (0)
where cn ∼ O(V m ) and cn is some (time-independent) initial state. The
programme to complete this series expansion is straightforward but technical.

$ Info. In the interaction representation, the state |ψ(t)!I can be related to

an inital state |ψ(t0 )!I through the time-evolution operator, UI (t, t0 ), i.e. |ψ(t)!I =
UI (t, t0 )|ψ(t0 )!I . Since this is true for any initial state |ψ(t0 )!I , from Eq. (12.1), we
must have

i!∂t UI (t, t0 ) = VI (t)UI (t, t0 ) ,

with the boundary condition UI (t0 , t0 ) = I. Integrating this equation from t0 to t,

formally we obtain,
%
i t "
UI (t, t0 ) = I − dt VI (t" )UI (t" , t0 ) .
! t0

This result provides a self-consistent equation for UI (t, t0 ), i.e. if we take this expres-
sion and substitute UI (t" , t0 ) under the integrand, we obtain
% t # $2 % t % t!
i i
UI (t, t0 ) = I − dt" VI (t" ) + − dt" VI (t" ) dt"" VI (t"" )UI (t"" , t0 ) .
! t0 ! t0 t0

Iterating this procedure, we thus obtain

"∞ # $n % t % tn−1
i
UI (t, t0 ) = − dt1 · · · dtn VI (t1 )VI (t2 ) · · · VI (tn ) , (12.3)
n=0
! t0 t0

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12.2. TIME-DEPENDENT PERTURBATION THEORY 142

where the term n = 0 translates to I. Note that the operators VI (t) are organised in
a time-ordered sequence, with t0 ≤ tn ≤ tn−1 ≤ · · · t1 ≤ t. With this understanding,
we can write this expression more compactly as
& i Rt ! ! '
− dt VI (t )
UI (t, t0 ) = T e ! t0 ,

where “T” denotes the time-ordering operator and its action is understood by Eq. (12.3).

If a system is prepared in an initial state, |i! at time t = t0 , at a subsequent

time, t, the system will be in a final state,

cn (t)
" ( )* +
|i, t0 , t! = UI (t, t0 )|i! = |n! "n|UI (t, t0 )|i! .
n
!
Making use of Eq. (12.3), and the resolution of identity, m |m!"m| = I, we
obtain

c(0)
n c(1)
n c(2)
n
()*+ ( )* +( )* +
% t % t % t! "
i 1
cn (t) = δni − dt" "n|VI (t" )|i! − 2 dt" dt"" "n|VI (t" )|m!"m|VI (t"" )|i! + · · · .
! t0 ! t0 t0 m

Recalling that VI = eiĤ0 t/!V e−iĤ0 t/!, we thus find that

%
i t " iωni t!
n (t) = −
c(1) dt e Vni (t" )
! t0
% % ! (12.4)
1 " t " t "" iωnm t! +iωmi t!!
cn (t) = − 2
(2)
dt dt e Vnm (t" )Vmi (t"" ) ,
! m t0 t0

where Vnm (t) = "n|V (t)|m! and ωnm = (En − Em )/!, etc. In particular, the
probability of effecting a transition from state |i! to state |n! for n &= i is given
(1) (2)
by Pi→n = |cn (t)|2 = |cn (t) + cn (t) + · · · |2 .

$ Example: The kicked oscillator: Suppose a simple harmonic oscillator is

prepared in its ground state |0! at time t = −∞. If it is perturbed by a small time-
2 2
dependent potential V (t) = −eEx e−t /τ , what is the probability of finding it in the
first excited state, |1!, at t = +∞?
Working to the first order of perturbation theory, the probability is given by
(1) (1) ,t ! !2 2
P0→1 * |c1 |2 where c1 (t) = − !i t0 dt" eiω10 t V10 (t" ), V10 (t" ) = −eE"1|x|0!e−t /τ
and ω10 = ω. Using the ladder operator
- - formalism, with |1! = a† |0! and x =
! !
(a + a† ), we have "1|x|0! = 2mω . Therefore, making use of the identity
, ∞2mω " 2 √
−∞
dt exp[iωt" − t" /τ 2 ] = πτ exp[−ω 2 τ 2 /4], we obtain the transition amplitude,
(1) . π −ω2 τ 2 /4
c1 (t → ∞) = ieEτ 2m!ω e . As a result, we obtain the transition probabil-
−ω 2 τ 2 /2
ity, P0→1 * (eEτ ) (π/2m!ω)e
2
. Note that the probability is maximized for
τ ∼ 1/ω.

$ Exercise. Considering the same perturbation, calculate the corresponding

transition probability from the ground state to the second excited state. Hint: note
that this calculation demands consideration of the second order of perturbation theory.

Advanced Quantum Physics

12.3. “SUDDEN” PERTURBATION 143

12.3 “Sudden” perturbation

To further explore the time-dependent perturbation theory, we turn now to
consider the action of fast or “sudden” perturbations. Here we define sudden
as a perturbation in which the switch from one time-independent Hamiltonian
Ĥ0 to another Ĥ0" takes place over a time much shorter than any natural
period of the system. In this case, perturbation theory is irrelevant: if the
system is initially in an eigenstate |n! of Ĥ0 , its time evolution following the
switch will follow that of Ĥ0" , i.e. one simply
! has to expand the initial state as
a sum over the eigenstates of Ĥ0" , |n! = n! |n" !"n" |n!. The non-trivial part
of the problem lies in establishing that the change is sudden enough. This is
achieved by estimating the actual time taken for the Hamiltonian to change,
and the periods of motion associated with the state |n! and with its transitions
to neighboring states.

12.3.1 Harmonic perturbations: Fermi’s Golden Rule

Let us then consider a system prepared in an initial state |i! and perturbed by
a periodic harmonic potential V (t) = V e−iωt which is abruptly switched on at
time t = 0. This could represent an atom perturbed by an external oscillating
electric field, such as an incident light wave. What is the probability that, at
some later time t, the system lies in state |f!?
From Eq. (12.4), to first order in perturbation theory, we have
%
(1) i t
! i ei(ωfi −ω)t − 1
cf (t) = − dt" "f|V |i!ei(ωfi −ω)t = − "f|V |i! .
! 0 ! i(ωfi − ω)
The probability of effecting the transition after a time t is therefore given by
# $2 Plot of sin2 (αt)/α2 for t = 1.
(1) 1 2 sin((ωfl − ω)t/2) Note that, as t → ∞, this func-
Pi→f (t) * |cf (t)| = 2 |"f|V |i!|
2
. tion asymptotes to a δ-function,
! (ωfl − ω)/2
πtδ(α).
Setting α = (ωfl − ω)/2, the probability takes the form sin2 (αt)/α2 with a
peak at α = 0, with maximum value t2 and width of order 1/t giving a total
weight of order t. The function has more peaks positioned at αt = (n + 1/2)π.
Enrico Fermi 1901-1954:
These are bounded by the denominator at 1/α2 . For large t their contribution An Italian physi-
comes from a range of order 1/t also, and as t → ∞ the function tends towards cist most noted
a δ-function centred at the origin, but multiplied by t, i.e. the likelihood of for his work on
the development
transition is proportional to time elapsed. We should therefore divide by t to of the first
get the transition rate. ,∞
nuclear reactor,
and for his
Finally, with the normalisation, −∞ dα( sin(αt)
α ) = πt, we may effect the
2
contributions to
replacement, limt→∞ 1t ( sin(αt)
α ) = πδ(α) = 2πδ(2α) leading to the following
2 the development
of quantum
expression for the transition rate, theory, nuclear and particle physics,
and statistical mechanics. Fermi was
awarded the Nobel Prize in Physics
Pi→f (t) 2π
Ri→f (t) = lim = 2 |"f|V |i!|2 δ(ωfl − ω) . (12.5) in 1938 for his work on induced
t→∞ t ! radioactivity and is today regarded
as one of the most influential
scientists of the 20th century. He is
This expression is known as Fermi’s Golden Rule.2 One might worry that, acknowledged as a unique physicist
in the long time limit, we found that the probability of transition is in fact who was highly accomplished in both
theory and experiment. Fermium, a
2 synthetic element created in 1952 is
Curiously, although named after Fermi, most of the work leading to the Golden Rule was
undertaken in an earlier work by Dirac, (P. A. M. Dirac, The quantum theory of emission and named after him.
absorption of radiation. Proc. Roy. Soc. (London) A 114, 243265 (1927)) who formulated
an almost identical equation, including the three components of a constant, the matrix
element of the perturbation and an energy difference. It is given its name due to the fact
that, being such a useful relation, Fermi himself called it “Golden Rule No. 2” (E. Fermi,
Nuclear Physics, University of Chicago Press, 1950).

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12.3. “SUDDEN” PERTURBATION 144

diverging — so how can we justify the use of perturbation theory? For a

transition with ωfl &= ω, the “long time” limit is reached when t - 1/(ωfl − ω),
a value that can still be very short compared with the mean transition time,
which depends on the matrix element. In fact, Fermi’s Rule agrees extremely
well with experiment when applied to atomic systems.

$ Info. Alternative derivation of the Golden Rule: When light falls on

an atom, the full periodic potential is not suddenly imposed on an atomic time scale,
but builds up over many cycles (of the atom and of the light). If we assume that
V (t) = eεt V e−iωt , with ε very small, V is switched on very gradually in the past, and
we are looking at times much smaller than 1/ε. We can then take the initial time to
be −∞, that is,
%
(1) i t ! 1 ei(ωfl −ω−iε)t
cf (t) = − "f|V |i!ei(ωfl −ω−i%)t dt" = − "f|V |i! ,
! −∞ ! ωfl − ω − iε
2εt
d (1)
i.e. |cf (t)|2 = !12 (ωfl −ω)
e
2 +ε2 |"f|V |i!| . Applied to the transition rate
2
dt |cf (t)| ,
2
the
identity limε→0 (ωfl −ω)2 +ε2 → 2πδ(ωfl − ω) leads to the Golden Rule.
2ε

From the expression for the Golden rule (12.5) we see that, for transitions to
occur, and to satisfy energy conservation:

(a) the final states must exist over a continuous energy range to match ∆E =
!ω for fixed perturbation frequency ω, or
(b) the perturbation must cover a sufficiently wide spectrum of frequency so
that a discrete transition with a fixed ∆E = !ω is possible.

For two discrete states, since |Vfi |2 = |Vif |2 , we have the semiclassical result
Pi→f = Pf→i – a statement of detailed balance.

12.3.2 Info: Harmonic perturbations: second-order transi-

tions
Although the first order perturbation theory is often sufficient to describe
transition probabilities, sometimes first order matrix element, "f|V |i! is iden-
tically zero due to symmetry (e.g. under parity, or through some selection rule,
etc.), but other matrix elements are non-zero. In such cases, the transition
may be accomplished by an indirect route. We can estimate the transition
probabilities by turning to the second order of perturbation theory (12.4),
% % !
(2) 1 " t " t "" iωfm t! +iωmi t!!
cf (t) = − 2 dt dt e Vfm (t" )Vmi (t"" ) .
! m t0 t0

If, as above, we suppose that a harmonic potential perturbation is gradu-

ally switched on, V (t) = eεt V e−iωt , with the initial time t0 → −∞, we have
% t % t!
(2) 1 " ! !!
cf (t) = − 2 "f|V |m!"m|V |i! dt" dt"" ei(ωfm −ω−iε)t ei(ωmi −ω−iε)t .
! m −∞ −∞

The integrals are straightforward, and yield

1 i(ωfi −2ω)t e2εt " "f|V |m!"m|V |i!
n =−
c(2) e .
! 2 ωfi − 2ω − 2iε m ωm − ωi − ω − iε

Then, following our discussion above, we obtain the transition rate:

/ /2
d (2) 2 2π //" "f|V |m!"m|V |i! //
|c | = 4 / / δ(ωfi − 2ω).
dt n ! / m ωm − ωi − ω − iε /

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12.3. “SUDDEN” PERTURBATION 145

This is a transition in which the system gains energy 2!ω from the harmonic
perturbation, i.e. two “photons” are absorbed in the transition, the first taking
the system to the intermediate energy ωm , which is short-lived and therefore
not well defined in energy – indeed there is no energy conservation requirement
for the virtual transition into this state, only between initial and final states.
Of course, if an atom in an arbitrary state is exposed to monochromatic light,
other second order processes in which two photons are emitted, or one is
absorbed and one emitted (in either order) are also possible.

Advanced Quantum Physics

Chapter 13

Radiative transitions

Previously, we have addressed the quantum theory of atoms coupled to a clas-

sical time-independent electromagneic field, cf. our discussion of the Zeeman
and Stark effects. However, to develop a complete quantum mechanical de-
scription of light-matter interaction, we have to address both the quantum
theory of the electromagnetic field and the coupling of light to matter. In the
following section, we will address both of these issues in turn. Our motivation
for developing such a consistent theory is that it will (a) provide us with a
platform to address the problem of radiative transitions in atoms and (b) it
forms the basis of the field of quantum optics.

13.1 Coupling of matter to the electromagnetic field

Let us then consider the Hamiltonian of a single-electron atom subject to a
time-dependent external electromagnetic field,
1
Ĥatom = (p̂ + eA(r, t))2 − eφ(r, t) + V (r) .
2m
Here V (r) denotes the binding potential associated with the atomic nucleus.
To keep our discussion of a complex problem as simple as possible, we have fo-
cussed on the single electron system. However, a generalization of the method-
ology to multi-electron atoms would not present significant challenges. Ex-
panding the kinetic energy, the atomic Hamiltonian can be recast as Ĥatom =
Ĥ0 + Ĥpara + Ĥdia. , where

p̂2
Ĥ0 = + V (r) ,
2m
denotes the usual non-interacting Hamiltonian of the isolated atom,
e
Ĥpara (t) = A(t) · p̂ ,
m
represents the time-dependent paramagnetic term arising from the coupling of
the electron to the electromagnetic field, and Ĥdia = (eA)2 /2m represents the
diamagnetic term. Since we will be interested in the absorption and emission
of single photons, we can neglect the influence of diamagnetic term which
presents only a tiny perturbation in the atomic system.
Previously, in chapter 11.2, we have see that the quantum Hamiltonian for
the electromagnetic field can be expressed as,
! " #
1
Ĥrad = !ωk a†kλ akλ + ,
2
k,λ=1,2

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13.1. COUPLING OF MATTER TO THE ELECTROMAGNETIC FIELD 147

where the operators a†kλ and akλ create and annihilate photons with wavevec-
tor k and polarization λ, and ωk = c|k|. These ladder operators obey the
(bosonic) commutation relations, [akλ , a†k! λ! ] = δk,k! δλ,λ! , with [akλ , ak! λ! ] =
[a†kλ , a†k! λ! ] = 0, and act on photon number states as
√
akλ |nkλ " = nkλ |nkλ − 1"
√
a†kλ |nkλ " = nkλ + 1|Nkλ + 1" .

Here |nkλ " represents a photon number state with nk,λ photons in the mode
(kλ). Finally, in the Heisenberg representation, we have seen that the vector
potential can be expanded in field operators as
$
! ! % &
A(r, t) = êkλ akλ ei(k·r−ωk t) + ê∗kλ a†kλ e−i(k·r−ωk t) .
2%0 ωk V
k,λ

Taken together, Ĥ = Ĥ0 + Ĥrad + Ĥpara (t) specify the full quantum mechanical
Hamiltonian of the atom light system.

13.1.1 Spontaneous emission

With this background, let us now consider the probability for an atom, initially
in a state |i" to make a transition to a state |f" leading to the emission of a
photon of wavevector k and polarization λ – a process of spontaneous emission.
If we suppose that the radiation field is initially prepared in the vacuum state,
|0", then the final state involves one photon, |kλ" = a†kλ |0". Therefore, making
use of Fermi’s Golden rule (12.5), with the perturbation Ĥpara = m e
Â(t) · p̂,
we have the transition probability
Schematic showing spontaneous
2π emission from an initial state at
Γi→f (t) = |$f| ⊗$ kλ|Ĥpara |i" ⊗ |Ω"|2 δ(ωif − ωk )
!2 energy Ei = E2 to a final state
at energy Ef = E1 .
where ωif = (Ei − Ef )/!. Then substituting the field operator expansion of Â,
we have
' $ '2
2π '' e ! '
'
Γi→f,kλ = '$f| ⊗$ Ω|akλ ê∗kλ a†kλ e−ik·r · p̂|i" ⊗ |Ω"' δ(ωif − ωk )
! ' m 2%0 ωk V '

As a result, we finally obtain

' $ '2
2π ' e ! '
' ∗ −ik·r '
Γi→f,kλ = '$f| êkλ e · p̂|i"' δ(Ei − Ef − !ωk )
! ' m 2%0 ωk V '

To determine the transition rate, we have to analyse matrix elements of the

form $f|eik·r ê∗kλ · p̂|i". Let us begin by estimating its magnitude. For a typical
atomic state, $ê∗kλ · p̂" & p & Zmcα, where we have included a general nuclear
charge, Z. But what about the exponential factor? With r ∼ !/p & !/mZcα,
p2
and ωk = c|k| & 2m (for electronic transitions), we have

ωk ! !p
k·r& & & Zα .
c p mc
This means that, for Zα ( 1, we can expand the exponential as a power
series in k · r with the lowest terms being dominant. Taking the zeroth order
term, and making use of the operator identity, p̂ = !i [Ĥ0 , r] which follows from

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13.1. COUPLING OF MATTER TO THE ELECTROMAGNETIC FIELD 148

the Heisenberg equations of motion for operators, the matrix element may be
written as
i Ef − Ei ∗
$f|ê∗kλ · p̂|i" = mê∗kλ · $f| [Ĥ0 , r]|i" = im êkλ · $f|r|i" = −imωk $f|ê∗kλ · r|i" .
! !
This result, which emerges from the leading approximation in Zα, is known
as the electric dipole approximation. Effectively, we have set (exercise)

e
Â(r, t) · p̂ & eÊ(r, t) · r ,
m

translating to the potential energy of a dipole, with moment d = −er, in an

oscillating electric field.

13.1.2 Absorption and stimulated emission

Let us now consider the absorption of a photon with wave number, k, and
polarization, λ. If we assume that, in the initial state, there are nkλ photons
in state (kλ) then, after the transition, there will be nkλ − 1. Then, if the
initial state of the atom is i" and the final state is |f", the transition amplitude
involves the matrix element,

$f| ⊗$ (nk,λ − 1)|Ĥpara |i" ⊗ |nkλ "

$
e !
= $f| ⊗$ (nk,λ − 1)| êkλ akλ eik·r · p̂|i" ⊗ |nkλ "
m 2%0 ωk V
√
Then, using the relation akλ |nkλ " = nkλ |(nkλ − 1)",
$ Schematic showing absorption
e !nkλ ik·r from an initial state at energy
$f| ⊗$ (nk,λ − 1)|Ĥpara |i" ⊗ |nkλ " = $f| e êkλ · p̂|i" Ei = E1 to a final state at en-
m 2%0 ωk V ergy Ef = E2 .

As a result, using Fermi’s Golden rule, we obtain the transition amplitude,

' $ '2
2π ' e !nkλ ik·r '
' '
Γi→f,kλ = '$f| e êkλ · p̂|i"' δ(Ef − Ei − !ωk )
! ' m 2%0 ωk V '

In particular, we find that the absorption rate increases linearly with photon
number, nkλ .
Similarly, if we now consider the emission process in which there is are
already nk,λ photons in the initial state, we have the revised transition rate,
Schematic showing the stimu-
' $ '2
' ' lated emission from an initial
2π '' e !(nk,λ + 1) −ik·r ∗ '
state at energy Ei = E2 to a final
Γi→f,kλ = ' $f| e êkλ · p̂|i"'' δ(Ef − Ei − !ωk ) .
! ' m 2%0 ωk V ' state at energy Ef = E1 .

This enhancement of the transition rate by the photon occupancy is known as

stimulated emission.
Altogether, in the dipole approximation, we have the transition rates,
(
πωk nkλ δ(Ef − Ei − !ωk ) absorption
Γi→f,kλ = |$f|êkλ · d|i"|2
%0 V (nkλ + 1) δ(Ei − Ef − !ωk ) emission

If there are no photons present initially, this expression reduces to that ob-
tained from spontaneous emission. The nkλ -independent component of the

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13.1. COUPLING OF MATTER TO THE ELECTROMAGNETIC FIELD 149

expression for absorption and emission coincide, an equality known as de-

tailed balance.
If we are interested in the total rate, dΓλ at which photons of)polarization λ
are scattered into the solid angle dΩ, we must compute dRλ = k∈dΩ Γi→f,kλ .
Since, in)the elemental* volume d3 k = k 2 dk dΩ, there are d3 kV /(2π)3 states, we
may set k = (2π)3 k 2 dk dΩ. Finally, if we assume that the photon occupa-
V

tion of state (kλ) is isotropic, dependent only on |k|, we find that the integrated
* k2 dk
transition rate per unit solid angle is given by dR dΩ = V
λ
Γ
(2π)3 i→f,kλ
from
which we obtain
(
dRλ 1 ω3 nλ (ω) absorption
= |$f|êkλ · d|i"|2
dΩ 4π%0 2π!c3 nλ (ω) + 1 emission

Here, in carrying out the integral, we have used the relation ωk = c|k| and
!ω = |Ef − Ei |. For a thermal distribution of photons, with the energy density
specified by the Planck formula,

!ω 3 1
u(ω) = n̄λ (ω), n̄λ (ω) = ,
πc3 e!ωk /kB T −1
this equates a stimulated absorption/emission rate,

dRλ 1 1
= |$f|êkλ · d|i"|2 u(ω)
dΩ 4π%0 2!2

From these expressions, we can obtain the power loss as Pλ = !ωRλ . Before
discussing the selection rules implied by the form of the dipolar coupling, it is
first helpful to digress and discuss connections of this result to a famous result
due to Einstein.

( Info. Einstein’s A and B coefficients: In fact, the frequency dependence

of the spontaneous emission rate can be inferred without invoking quantum field the-
oretic methods by means of an ingenious argument due to Einstein which showed that
the stimulated and spontaneous transitions must be related. Consider an ensemble
of atoms exposed to a black-body radiation field at temperature T . Let us consider
transitions between two states |ψj " and |ψk ", with Ek − Ej = !ω. Suppose the num-
bers of atoms in the two states are nj and nk . The possible transitions and their rates
per atom are given by:

absorption j→k Bj→k u(ω)

stimulated emission k→j Bk→j u(ω)
spontaneous emission k→j Ak→j (ω)

where u(ω), the energy density of radiation per unit ω. A and B are known as
Einstein’s A and B coefficients, and, as we have seen, are properties of the atomic
states concerned.
Now, in thermodynamic equilibrium, the rates must balance, so that

nk [Ak→j (ω) + Bk→j u(ω)] = nj Bj→k u(ω) .

At the same time, the relative populations of the two states (assumed non-degenerate
for simplicity), are given by a Boltzmann factor

nj e−Ej /kB T
= −E /k T = e!ω/kB T .
nk e k B
Thus we have: + ,
Ak→j (ω) = Bj→k e!ω/kB T − Bk→j u(ω) . (13.1)

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13.2. SELECTION RULES 150

For a black-body, the energy density u(ω) is just given by Planck’s formula, u(ω) =
!ω 3
π 2 c3 e!ω/kB T −1 . The Ak→j coefficient in Eq. (13.1) certainly cannot depend on tem-
1

perature, so T must cancel on the right hand side. Hence,

!ω 3
Bk→j = Bj→k and Ak→j (ω) = Bk→j .
π 2 c3
So, the A and B coefficients are related, and if we can calculate the B coefficient for
stimulated emission from Fermi’s golden rule, we can infer A, and vice versa.

13.2 Selection Rules

It is clear from the formulae for the transition rates that no transition, either
spontaneous or stimulated, will occur between the states |i" and |f" unless at
least one component of the dipole transition matrix element $f|d̂|i" is non-
zero. It is often possible to show that the matrix elements are zero for certain
pairs of states. If so, the transition is not allowed (at least in the electric
dipole approximation), and the results can often be summarised in terms of
simple selection rules governing the allowed changes in quantum numbers
in transitions.
Since the dipole operator d̂ = qr changes sign under parity (r → −r), the
matrix element $f|d̂|i" will trivially vanish if the states |f" and |i" have the
same parity. Therefore, the parity of the wavefunction must change in
an electric dipole transition.
Moreover, in the absence of spin-orbit interaction, since the wavefunction
can be separated into spatial and spin components, |f" = |φf " ⊗ |χf ", with χf
being the spin wavefunction, and the dipole operator only acts on the spatial
part of the wavefunction, so the matrix element becomes
-
$f|d̂|i" = $χf |χi " d3 r φ∗f (r) qrφi (r) .

The spin term $χf |χi " (and therefore the matrix element) vanishes unless |χi "
and |χf " are identical. This can be expressed by the selection rule

∆s = 0, ∆ms = 0 .

The spin state is not altered in an electric dipole transition.

Let us now consider the selection rules for the orbital angular momenta.
From the operator identity, [L̂i , rj ] = i!%ijk rk (exercise), it follows that

[L̂z , z] = 0, [L̂z , x ± iy] = ±(x ± iy)! ,

We therefore obtain the relation,

$+% , m% |[L̂z , z]|+, m" = (m% − m)!$+% , m% |z|+, m" = 0 .

Similarly, since $+% , m% |[L̂z , x ± iy]|+, m" = ±$+% , m% |x ± iy|+, m", it follows that

(m% − m ∓ 1)$+% , m% |x ± iy|+, m" = 0 .

Therefore, to get non-zero component of the dipole matrix element, we require.

∆m$ = 0, ±1 .

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13.2. SELECTION RULES 151

Similarly, using operator identity [L̂2 , [L̂2 , r]] = 2!2 (rL̂2 + L̂2 r) (exercise),
we have

$+% , m% |[L̂2 , [L̂2 , r]]|+, m" = [+% (+% + 1) − +(+ + 1)]2 $+% , m% |r|+, m"
= 2[+% (+% + 1) + +(+ + 1)]$+% , m% |r|+, m"

i.e. (+ + +% )(+ + +% + 2)[(+% − +)2 − 1]$+% , m% |r|+, m" = 0. Since +, +% ≥ 0, we can

conclude that, to effect an electric dipole transition, we must have

∆+ = ±1 .

One may summarize the selection rules for + and m$ is by saying that the
photon carries off (or brings in, in an absorption transition) one unit of angular
momentum. It should be noted, however, that these rules were derived for the
specific case of an electric dipole transition of the system. It is possible, though
much less likely in the case of an atom, for the electromagnetic field to interact
with some other observable such as the magnetic dipole moment or the electric
quadrupole moment. In such transitions the selection rules are different. For
example, the magnetic dipole operator is µ̂ = −µB L̂/! (or −2µB Ŝ/! for the
spin) and since the angular momentum does not change sign under the parity
transformation, there is no change of parity in a magnetic dipole transition. To
avoid confusion, we shall continue to confine the discussion to electric dipole
transitions, which are responsible for the prominent lines in atomic spectra.
For transitions with ∆m$ = 0, the dipole matrix element $f|d|i" ∼ êz and
there is no component of polarization along z-direction. Similarly, for electric
dipole transitions with m% = m ± 1, $+% , m% |x ∓ iy|+, m" = 0 = $+% , m% |z|+, m",
and $f|d|i" ∼ (1, ∓i, 0). In this case, if the wavevector of photon lies along
z, the emitted light is circularly polarized with a polarization which depends
on helicity. Conversely, if the wavevector lies in xy place, the emitted light is
linearly polarized, while in general the polarization is elliptical.
Finally, in the presence of spin-orbit coupling, stationary states are labelled
by quantum numbers J, mJ , +, s where Ĵ = L̂ + Ŝ. In this case, the selection
rules can be inferred by looking for the conditions for non-zero matrix elements
$J % , mJ ! , +% , s% |r|J, mJ , +, s". By expanding states |J, mJ , +, s" in the basis states
|+, m$ "⊗|s, ms ", one may uncover the following set of selection rules: For dipole
transitions to take place, we require that

∆mj = 0, ±1 ∆j = 0, ±1 not 0→0

( Info. As another example of selection rules, consider a charged particle moving

in a one-dimensional harmonic potential. The wavefunctions are characterised by the
quantum number n, so the state |n" corresponds to energy (n+1/2)!ω. An oscillating
electric field in the x-direction can induce transitions between states |n" and |n# ",
governed by matrix elements of the form . $n# | x |n". These can be evaluated by use of
!
the ladder operators â and ↠. Since x = 2mω (a + a ),
†
the matrix element becomes
/
! 0√ √ 1
$n | x |n" =
#
n + 1$n# |n + 1" + n$n# |n − 1" ,
2mω
and therefore vanishes unless n = n# ± 1. Hence the selection rule, in the electric
dipole approximation, is ∆n = ±1.

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13.3. LASERS 152

13.3 Lasers
Finally, to close this section, we will consider a principle application of light Arthur Leonard Schawlow 1921-
matter interaction – the laser. The laser provides a light source which enables 1999
modern spectroscopy. The term “laser” is an acronym for “light amplification American
physicist and
by stimulated emission of radiation”. However, a laser not only amplifies light, corecipient, with
but it acts as a special kind of light source which is characterised by a number Nicolaas Bloem-
bergen of the US
of properties: and Kai Manne
Monochromaticity: The emission of the laser generally corresponds to Borje Siegbahn
just one of the atomic transitions of the gain medium (in contrast to discharge of Sweden, of
the 1981 Nobel
lamps, which emit on all transitions). The spectral line width can be much Prize for Physics for his work in
smaller than that of the atomic transition. This is because the emission is developing the laser and in laser
spectroscopy. In 1949 he went to
affected by the optical cavity. In certain cases, the laser can be made to Columbia University, where he began
operate on just one of the modes of the cavity. Since the Q of the cavity1 collaborating with Charles Townes on
the development of masers, lasers,
is generally rather large, the mode is usually much narrower than the atomic and laser spectroscopy. Schawlow
transition, and the spectral line width is orders of magnitude smaller than the worked on the project that led to
atomic transition. the construction of the first working
maser in 1953 (for which Townes
Coherence: In discussing the coherence of an optical beam, we must received a share of the 1964 Nobel
distinguish between spatial and temporal coherence – laser beams have a high Prize for Physics). Schawlow was a
research physicist at Bell Telephone
degree of both. Spatial coherence refers to whether there are irregularities in Laboratories from 1951 to 1961.
the optical phase in a cross-sectional slice of the beam. Temporal coherence In 1958 he and Townes published
a paper in which they outlined
refers to the time duration over which the phase of the beam is well defined. the working principles of the laser,
In general, the temporal coherence time, tcoh is given as the reciprocal of the though the first such working device
spectral line width, ∆ν. Thus the coherence length +coh is given by, was built by another American
physicist, Theodore Maiman, in
c 1960. In 1961 Schawlow became
+coh = ctcoh = . a professor at Stanford University.
∆ν He became a world authority on
laser spectroscopy, and he and
Typical values of the coherence length for a number of light sources are given Bloembergen earned their share
in the table below: of the 1981 Nobel Prize by using
lasers to study the interactions
of electromagnetic radiation with
Source ∆ν (Hz) tcoh (s) +coh (m) matter.
Na discharge lamp 5 × 1011 2 × 10−12 6 × 10−4
(D-lines at 589nm)
Multi-mode HeNe laser 1.5 × 109 6 × 10−10 0.2
(632.8nm line)
Single-mode HeNe laser 1 × 106 1 × 10−6 300
(632.8nm line)

These figures explain why it is much easier to conduct interference experiments

with a laser than with a discharge lamp. If the path difference exceeds +coh
you will not get interference fringes, because the light is incoherent.
Brightness: The brightness of lasers arises from two factors. First of all,
the fact that the light is emitted in a well-defined beam means that the power
per unit area is very high, even though the total amount of power can be
rather low. Then we must consider that all the energy is concentrated within
the narrow spectrum of the active atomic transition. This means that the
spectral brightness (i.e. the intensity in the beam divided by the width of the
emission line) is even higher in comparison with a white light source like a
light bulb. For example, the spectral brightness of a 1 mW laser beam could
easily be millions of time greater than that of a 100 W light bulb.
Ultra-short pulse generation: In some cases, lasers can be made to
operate in pulses. The time duration of the pulses tp is linked to the spectral
1
Recall that the Q-factor is approximately the number of oscillations required for a freely
oscillating system’s energy to fall by a factor of 1/e2π of its original energy.

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13.3. LASERS 153

band width of the laser light ∆ν by the “uncertainty” product ∆t∆ν ∼ 1.

This follows from taking the Fourier transform of a pulse of duration tp . As
an example, the bandwidth of the 632.8nm line in the HeNe laser is 1.5 GHz
(see above), so that the shortest pulses that a HeNe laser can produce would
be 0.67 ns long. This is not particularly short by modern standards. Dye
lasers typically have gain bandwidths greater than 1013 Hz, and can be used
to generate pulses shorter than 100fs. This is achieved by a technique called
“mode-locking”. These short pulsed lasers are very useful for studying fast
processes in physics, chemistry and biology.

13.3.1 Operating principles of a laser

Light amplification is achieved by stimulated emission. Ordinary optical mate-
rials do not amplify light. Instead, they tend to absorb or scatter the light, so
that the light intensity out of the medium is less than the intensity that went
in. To get amplification you have to drive the material into a non-equilibrium
state by pumping energy into it. Positive optical feedback is achieved by in-
serting the amplifying medium inside a resonant cavity. Light in the cavity
passes through the gain medium and is amplified. It then bounces off the end
mirrors and passes through the gain medium again, getting amplified further.
This process repeats itself until a stable equilibrium condition is achieved when
the total round trip gain balances all the losses in the cavity.
The losses in the cavity fall into two categories: useful, and useless. The
useful loss comes from the output coupling. One of the mirrors (called the
“output coupler”) has reflectivity less than unity, and allows some of the light
oscillating around the cavity to be transmitted as the output of the laser.
The value of the transmission is chosen to maximise the output power. If the
transmission is too low, very little of the light inside the cavity can escape, and
thus we get very little output power. On the other hand, if the transmission
is too high, there may not be enough gain to sustain oscillation, and there
would be no output power. The optimum value is somewhere between these
two extremes. Useless losses arise from absorption in the optical components
(including the laser medium), scattering, and the imperfect reflectivity of the
other mirror (the “high reflector”).
In general we expect the gain to increase as we pump more energy into
the laser medium. At low pump powers, the gain will be small, and there will
be insufficient gain to reach the oscillation condition. The laser will not start
to oscillate until there is enough gain to overcome all the losses. This implies
that the laser will have a threshold in terms of the pump power.

13.3.2 Gain mechanism

Laser operation relies upon the phenomenon of stimulated emission. In a gas
of atoms in thermal equilibrium, the population of lower levels will always
be greater than the population of upper levels. Therefore, if a light beam is
incident on the medium, there will always be more upward transitions due
to absorption than downward transitions due to stimulated emission. Hence
there will be net absorption, and the intensity of the beam will diminish on
progressing through the medium.
To amplify the beam, we require that the rate of stimulated emission ex-
ceeds the rate of absorption. If the light beam is sufficiently intense that we can
ignore spontaneous emission, and the levels are non-degenerate, this implies
that the number of atoms in some upper level, N2 , must exceed that of the
lower level N1 . This is a highly non-equilibrium situation, and is called popu-

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13.3. LASERS 154

lation inversion. Once we have population inversion, we have a mechanism

for generating gain in the laser medium. The art of making a laser operate is
to work out how to get population inversion for the relevant transition.
To develop a theory of the laser threshold, we can consider separately the
rate equations for the photon and atomic excitation. Starting with photons, let
us consider excitations created by the transitions between just two levels of the
atom – a lower level 1, and an excited state 2. If the dipole matrix elements,
W , between the two levels are independent of position and frequency, the net
downwards transition rate is given by

W (N2 (n + 1) − N1 n)

where n denotes the total number of photons in the cavity, and N1,2 is the
number of atoms in states 1, 2. The first term represents the contribution
from stimulated and spontaneous emission, while the latter is associated with
absorption. Taking into account photon loss from the leaky cavity, the rate of
change of photon number is therefore given by

n
ṅ = DW n + N2 W − , (13.2)
τph

where D = N2 − N1 represents the population imbalance and 1/τph is the

photon loss rate. This equation shows that the gain in a laser medium is
directly proportional to the degree of population inversion. Laser operation
will occur when there is enough gain to overcome the losses in the cavity. This
implies that a minimum amount of population inversion must be obtained
before the laser will oscillate.
To achieve population inversion atoms must be “pumped” into the upper
level 2. This can be achieved by a variety of techniques: Lasers are classified as
being either three-level of four-level systems. In the following, we will consider
the case of a three-level laser, although four-level lasers are more common.
Examples of four-level lasers include Helium Neon or Nd:YAG. In a four-level
laser, the levels comprise the ground state (0), the two lasing levels (1 and 2),
and a fourth level (3) which is used as part of the pumping mechanism. In
the three-level system, such as the first laser, ruby, level 1 is the ground state,
and pumping is achieved by exiting atoms to level 3 with a bright flash lamp
or by an electrical discharge, and then allowing them to decay rapidly to level
2. In this case, the corresponding rate equations for the populations of levels
1 and 2 can be written as

Ṅ2 & −w21 N2 + w12 N1 − (N2 − N1 )W n & −Ṅ1 ,

where w12 , w21 denote the “effective” transition rates between states 1 and
2 due to the pumping via the third state, and we have dropped the small
contribution from spontaneous emission. From this equation, we can deduce
that N1 + N2 = N , a constant, i.e. the decay from state 3 is so rapid that its
population is always negligible. In this case, we obtain

D0 − D
Ḋ = − 2DW n . (13.3)
T

where D0 = N (w12 − w21 )/(w12 + w21 ) denotes the unsaturated inversion

(i.e. the degree of population inversion that would exist if there were no
photons in the cavity, n = 0) and 1/T = w12 + w21 .

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13.4. DRIVEN HARMONIC OSCILLATOR 155

In steady-state, ṅ = Ḋ = 0, and Eq. (13.3) translates to a population

imbalance,
D0
D ≡ N2 − N1 = .
1 + 2T W n
From this result, we find the steady state photon number is given by

D0 W − 1/τph
n= .
2T W/τph

When D0 > 1/W τph , the laser threshold condition, there is a rapid increase
in the number of photons in the cavity and the system starts lasing.
Although this analysis addresses the threshold conditions, it does not pro-
vide any insight into the coherence properties of the radiation field. In fact,
one may show that the radiation field generated by the laser cavity forms a
coherent or Glauber state. The proof of this statement and the coherence
properties that follow would take us too far into the realm of laser physics.
However, we can gain some insight into this statement by studying a toy ex-
ample.

13.4 Driven harmonic oscillator

Consider a quantum harmonic oscillator Hamiltonian driven by some external
classical field,
" # % &
† 1
Ĥ = !ω a a + + ! f ∗ (t)a + f (t)a† .
2
Here f (t), which represents an (as yet) arbitrary function of time, t, charac-
terises the coupling between the harmonic oscillator and the classical pump.
For example, if f (t) is real, the function couples directly to the displacement,
a + a† ∼ x. If the system is prepared in the ground state of the harmonic
oscillator, the perturbation drives the system into a coherent state.
To understand how, let us consider the time-evolution in the interaction
representation, i!∂t |ψ(t)"I = VI |ψ(t)"I where |ψ(t)"I = eiĤ0 t/!|ψ(t)"S and,
defining f˜ = f eiωt ,2
% & % &
VI (t) = eiĤ0 t/!! f ∗ (t)a + f (t)a† e−iĤ0 t/! = ! f˜∗ (t)a + f˜(t)a† .

To solve for the time-evolution operator, i!∂t UI (t) = VI UI (t), let us consider
the coherent state, |α" = Û (α)|0" where Û (α) = exp[αa† − α∗ a], where α =
α(t). Equivalently, making use of the BCH identity, the unitary operator may
be written as
∗ α/2 † ∗a
Û (α) = e−α eαa e−α .
† †
Then, taking the time derivative, and making use of the identity, [eαa , a]e−αa =
−α, one obtains
2 3
† ∗ i ∗
∂t Û (α) = α̇a − α̇ a + Im(α̇ α) Û (α) .
2
*t % %
Therefore, setting α(t) = −i 0 dt f˜(t ), we obtain the solution
+ ,
UI (t) = exp α(t)a† − α∗ (t)a + iϕ(t) ,
† †
2
Here we have made use of the identity (exercise), eiωta a ae−iωta a
= e−iωt a.

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13.4. DRIVEN HARMONIC OSCILLATOR 156

*t
where ϕ(t) = 0 dt% 12 Im(α̇∗ α).
*t
If the driving force f (t) = f0 e−iωt (with f0 real), we have α(t) = −i 0 dt% f0 =
−if0 t and ϕ(t) = 0 leading to the solution, UI (t) = exp[−if0 (a† + a)t]. There-
fore, if the system was prepared in the harmonic oscillator ground state |0" at
time t = 0, the solution at time t is given by |ψ(t)"I = exp[−if0 (a† + a)t]|0" =
2 †
e−(f0 t) /2 e−if0 a t |0". Then, reexpressed in the Schrödinger representation,
2 /2 −iωt a† t
|ψ(t)"S = e−iĤ0 t/!|ψ(t)"I = e−(f0 t) e−if0 e |0" .

As a result, we can conclude that a classical oscillatory force drives a system

prepared in the vacuum into a coherent state. Applied to an optical cavity, an
oscillating classical dipole generates a coherent state of light – the principle
that underlies the operation of a laser.

Advanced Quantum Physics

Chapter 14

Scattering theory

Almost everything we know about nuclei and elementary particles has been
discovered in scattering experiments, from Rutherford’s surprise at finding
that atoms have their mass and positive charge concentrated in almost point-
like nuclei, to the more recent discoveries, on a far smaller length scale, that
protons and neutrons are themselves made up of apparently point-like quarks.
More generally, the methods that we have to probe the properties of condensed
matter systems rely fundamentally on the notion of scattering. In this sec-
tion, we will provide a brief introduction to the concepts and methodology of
scattering theory.
As preparation for the quantum mechanical scattering problem, let us first
consider the classical problem. This will allow us to develop (hopefully a
revision!) some elementary concepts of scattering theory, and to introduce
some notation. In a classical scattering experiment, one considers particles
of energy E = 12 mv02 (mass m and asymptotic speed v0 ), incident upon a
target with a central potential V (r). For a repulsive potential, particles are
scattered through an angle θ (see figure). The scattering cross-section, σ,
can be inferred from the number of particles dn scattered into some element
of solid angle, dΩ, at angle (θ, φ), i.e. for an incident flux ji (number of
particles per unit time per
! unit area), dn! π = ji σ dΩ.
! 2πThe total cross-section is
then obtained as σT = dΩ σ(θ, φ) = 0 sin θdθ 0 dφ σ(θ, φ). The angle of
deflection of the beam depends on the impact parameter, b (see figure right).
We therefore have that dn = ji bdb dφ = ji σ sin θdθdφ and

b db
σ(θ, φ) = .
sin θ dθ

$ Example: Let us consider then the case of classical Coulomb scattering

from a repulsive potential V (r) = κr where κ > 0. From classical physics, we know
that the particle will follow a hyperbolic trajectory with

L2
r= ,
mκ(e cos ϕ − 1)

where r = (r, ϕ) parameterises the relative coordinates of the particle and target,1
2
and e = (1 + 2EL
κ2 m )
1/2
> 1 denotes the eccentricity. Since the potential is central, the
angular momentum L is conserved and can be fixed asymptotically by the condition
L = mv0 b.
To obtain the scattering angle, θ, we can use the relation above to find the limiting
angle, cos ϕ0 = 1/e, where ϕ0 = (π − θ)/2. We therefore have tan(θ/2) = cot ϕ0 =
1
Note that the angle ϕ is distinct form the azimuthal angle φ associated with the axis of
scattering.

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14.1. BASICS 158

√ mκ2 1/2
1/ e2 − 1 = ( 2EL2) = 2Eb .
κ
Then, from this relation, we obtain the cross-section
b db κ2 1
σ= = ,
sin θ dθ 16E 2 sin4 θ/2
known as the Rutherford formula.

14.1 Basics
Let us now turn to the quantum mechanical problem of a beam of particles
incident upon a target. The potential of the target, V (r), might represent that
experienced by a fast electron striking an atom, or an α particle colliding with
a nucleus. As in the classical problem, the basic scenario involves directing
a stream or flux of particles, all at the same energy, at a target and detect
how many particles are deflected into a battery of detectors which measure
angles of deflection. In principle, if we assume that all the in-going particles
are represented by wavepackets of the same shape and size, our challenge is
to solve the full time-dependent Schrödinger equation for such a wavepacket,
" #
!2 2
i!∂t Ψ(r, t) = − ∇ + V (r) Ψ(r, t) ,
2m
and find the probability amplitudes for out-going waves in different directions
at some later time after scattering has taken place. However, if the incident
beam of particles is switched on for times very long as compared with the time
a particle would take to cross the interaction region, steady-state conditions
apply. Moreover, if we assume that the wavepacket has a well-defined energy
(and hence momentum), so it is many wavelengths long, and we may consider
it a plane wave. Setting Ψ(r, t) = ψ(r)e−iEt/!, we may therefore look for
solutions ψ(r) of the time-independent Schrödinger equation,
" #
!2 2
Eψ(r) = − ∇ + V (r) ψ(r) ,
2m
subject to the boundary condition that the incoming component of the wave-
function is a plane wave, eik·x . Here E = p2 /2m = !2 k2 /2m denotes the
energy of the incoming particles while their flux is given by
! !k
j = −i (ψ ∗ ∇ψ − ψ∇ψ ∗ ) = .
2m m
In the one-dimensional geometry, the impact of a plane wave with the
localized target resulted in a portion of the wave being reflected and a portion
transmitted through the potential region. From energy conservation, we may
deduce that both components of the outgoing scattered wave are plane waves
with wavevector ±k, while the influence of the potential are encoded in the
amplitude of the reflected and transmitted beams, and a potential phase shift.
Both amplitudes and phase shifts are then determined by solving the time-
independent Schrödinger equation subject to the boundary conditions which
ensure energy and flux conservation. In the three-dimensional system, the
phenomenology is similar: In this case, the wavefunction well outside the
localized target region will involve a superposition of the incident plane wave
and the scattered (spherical wave),2
eikr
ψ(r) $ eik·r + f (θ, φ) ,
r
2
Here, by localized, we mean a potential which is sufficiently short-ranged. At this stage,
it is not altogether clear what constraint this implies. But it will turn out that it excludes
the Coulomb potential!

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14.1. BASICS 159

where the function f (θ, φ) records the relative amplitude and phase of the
scattered components along the direction (θ, φ) relative to the incident beam.

To place these ideas on a more formal footing, consider the following: If

we define the direction of the incoming wave k to lie along the z-axis, a plane
wave can be recast in the form of an incoming and an outgoing spherical wave,
∞
% &
i $ " e−i(kr−"π/2) ei(kr−"π/2)
e ik·r
= i (2+ + 1) − P" (cos θ) ,
2k r r
"=0

where P" (cos θ) = ( 2"+1 ) Y"0 (θ) denote the Legendre polynomials. If we
4π 1/2

assume that the potential perturbation, V (r) depends only on the radial coor-
dinate (i.e. that it is spherically symmetric) and that the number of particles
are conserved by the potential (the flux of incoming particles is matched by
the flux of outgoing),3 when the potential is sufficient short-ranged (decreasing
faster than 1/r), the scattering wavefunction takes the asymptotic form
∞
% &
i $ " e−i(kr−"π/2) ei(kr−"π/2)
ψ(r) $ i (2+ + 1) − S" (k) P" (cos θ) ,
2k r r
"=0

subject to the constraint |S" (k)| = 1 following from the conservation of particle
flux (i.e. S" (k) = e2iδ! (k) ). Physically, the incoming component of the spherical
wave is undisturbed by the potential while the separate components of the
outgoing spherical wave are subject to a set of phase shifts, δ" (k). Recast in
the form of a perturbation, the asymptotic form of the wavefunction can be
straightforwardly rewritten as

eikr
ψ(r) $ eik·r + f (θ) ,
r
where the second component of the wavefunction denotes the change in the
outgoing spherical wave due to the potential, and
∞
$
f (θ) = (2+ + 1)f" (k)P" (cos θ) , (14.1)
"=0

with the coefficents f" (k) = 2ik

1
(S" (k) − 1) defining the partial wave scat-
tering amplitudes.
The corresponding asymptotic flux is then given by
'" #∗ " #(
! eikr eikr
j = −i Re eik·r
+ f (θ) ∇ e ik·r
+ f (θ) .
m r r

In general, an expansion then leads to a formidible collection of contributing

terms. However, for most of these contributions, there remains an exponential
factor, e±ikr(1−cos θ) where θ denotes the angle between k and r. For r → ∞,
the small angular integration implied by any physical measurement leads to a
fast oscillation of this factor. As a result, such terms are strongly suppressed
and can be neglected. Retaining only those terms where the phase cancellation
is complete, one obtains,
!k !k |f (θ)|2
j= + êr + O(1/r3 ) .
m m r2
3
Note that this assumption is not innocent. In a typical high energy physics experiment,
the collision energies are high enough to lead to particle production.

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14.2. METHOD OF PARTIAL WAVES 160

The first term represents the incident flux, while the remainder describes the
radial flux of scattered particles. In particular, the number of particles crossing
the area that subtends a solid angle dΩ at the origin (the target) is given by

!k |f (θ)|2 2
j · êr dA = r dΩ + O(1/r) .
m r2
Dropping terms of order 1/r, negligible in the asymptotic limit, one thus
obtains the differential cross-section, the ratio of the scattered flux to the
incident flux, dσ = !k
m
j · êr dA = |f (θ)|2 dΩ, i.e.

dσ
= |f (θ)|2 .
dΩ
! !
The total cross-section is then
! given by σtot = dσ = |f (θ)|2 dΩ. Then,
making use of the identity dΩP" (cos θ)P"! (cos θ) = 2"+1
4π
δ""! , and Eq. (14.1)
one obtains (exercise)

∞
4π $
σtot = 2 (2+ + 1) sin2 δ" (k) .
k
"=0

In particular, noting that P" (1) = 1, from Eq. (14.1) it follows that Im f (0) =
4π σtot , a relation known as the optical theorem.
k

14.2 Method of partial waves

Having established the basic concepts for the scattering problem, we turn now
to consider operationally how the scattering characteristics can be computed.
Here, for simplicity, we will focus on the properties of a centrally symmetric
potential, V (r), where the scattering wavefunction, ψ(r) (and indeed that scat-
tering amplitudes, f (θ)) must be symmetrical about the axis of incidence, and
hence independent of the azimuthal angle, φ. In this case, the wavefunction
can be expanded in a series of Legendre polynomials,
∞
$
ψ(r, θ) = R" (r)P" (cos θ) .
"=0

Each term in the series is known as a partial wave, and is a simultaneous

eigenfunction of the angular momentum operators L̂2 and L̂z having eigenvalue
!2 +(+ + 1) and 0 respectively. Following standard spectroscopic notation, + =
0, 1, 2, · · · are referred to as s, p, d, · · · waves. The partial wave amplitudes,
f" are determined by the radial functions, R" (r), defined by
" #
2 +(+ + 1)
∂r2 + ∂r − − U (r) + k 2
R" (r) = 0 ,
r r2

where U (r) = 2mV (r)/!2 represents the effective potential.

$ Example: To develop the partial wave scattering method, we will consider

the problem of quantum scattering from an attractive square well potential,
U (r) = −U0 θ(R − r). In this case, the radial wave equation takes the form
" #
2 +(+ + 1)
∂r + ∂r −
2
+ U0 θ(R − r) + k R" (r) = 0 .
2
r r2

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14.2. METHOD OF PARTIAL WAVES 161

At high energies, many channels contribute to the total scattering amplitude. How-
ever, at low energies, the scattering is dominated by the s-wave (+ = 0) channel.
In this case, setting u(r) = rR0 (r), the radial equation takes the simple form,
(∂r2 + U0 θ(R − r) + k 2 )u(r) = 0, with the boundary condition that u(0) = 0. We
therefore obtain the solution
)
C sin Kr r<R
u(r) = ,
sin(kr + δ0 ) r > R

where K 2 = k 2 + U0 > k 2 . The continuity condition of the wavefunction and its

derivative at r = R translates to the relation K cot(KR) = k cot(kR + δ0 ). From this
expression, we obtain the + = 0 phase shift, δ0 = tan−1 ( K
k
tan(KR)) − kR,4 i.e.
k tan(KR) − K tan(kR)
tan δ0 (k) = ,
K + k tan(kR) tan(KR)
Then, unless tan(KR) = ∞ (see below), an expansion at low energy (small k) obtains
δ0 $ kR( tan(KR)
KR − 1), and the + = 0 partial cross-section,
* +2
4π 4π 1 4π 2 tan(KR)
σ0 = 2 sin δ0 (k) = 2
2
$ 2 δ0 = 4πR 2
−1 .
k k 1 + cot2 δ0 (k) k KR

From this result, we find that when tan(KR)

KR = 1, the scattering cross-section vanishes.
An expansion in small k obtains

1 1
k cot δ0 = − + r0 k 2 + · · · ,
a0 2
1/2
where a0 = (1 − tan γ
γ )R, with γ = U0 R, defines the scattering length, and r0 is
the effective range of the interaction. At low energies, k → 0, the scattering cross-
section, σ0 = 4πa20 is fixed by the scattering length alone. If γ ' 1, a0 is negative.
As γ is increased, when γ = π/2, both a0 and σ0 diverge – there is said to be a zero
energy resonance. This condition corresponds to a potential well that is just able Scattering wavefunction, u(r),
to support an s-wave bound state. If γ is further increased, a0 turns positive – as for three-dimensional square well
it would be for an effective repulsive interaction until γ = π when σ0 = 0 and the potential for kR = 0.1 and γ = 1
process repeats with the appearance of a second bound state at γ = 3π/2, and so on. (top), π/2 (middle) and 2 (bot-
More generally, the +-th partial cross-section tom). Note that the scattering
length, a0 changes from nega-
4π 1 tive to positive as system passes
σ" = (2+ + 1) ,
k 2 1 + cot2 δ" (k) through bound state.
takes its maximum value is there is an energy at which cot δ" vanishes. If this occurs
as a result of δ" (k) increasing rapidly through an odd multiple of π/2, the cross-section
exhibits a narrow peak as a function of energy and there is said to be a resonance.
Near the resonance,
ER − E
cot δ" (k) = ,
Γ(E)/2
where ER is the resonance energy. If Γ(E) varies slowly in energy, the partial cross-
section in the vicinity of the resonance is given by the Breit-Wigner formula,
Scattering phase shift for kR =
4π Γ (ER )/4
2 0.1 as a function of γ.
σ" (E) = (2+ + 1) . (14.2)
k2 (E − ER )2 + Γ2 (ER )/4
4
More generally, choosing the solution to be finite at the origin, we find that
R! (r) = N! (K)j! (Kr), r < R,
where N! (K) is a normalization constant. In the exterior region, the general solution can
be written as R! (r) = B! (k)[j! (kr) − tan δ! (k)η! (kr)]. Continuity of R! and the derivative
∂r R! at the boundary, r = R, lead to the following expression for the phase shifts
kj!! (kR)j! (KR) − Kj! (kR)j!! (KR)
tan δ! (k) = .
kη!! (kR)j! (KR) − Kη! (kR)j!! (KR)
Here j!! (x) = ∂x j! (x) and similarly η!! .

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14.3. THE BORN APPROXIMATION 162

$ Exercise. For a hard-core interaction, U (r) = U0 θ(R − r), with U0 → ∞,

show that at low energy δ0 = −kR. As k → 0, show that the differential cross-section
k→0
is isotropic and given by dΩ
dσ
= R2 and σtot → 4πR2 .

$ Info. Ultracold atomic gases provide a topical arena in which resonant scatter-
ing phenomena are exploited. In particular, experimentalists make use of Feshbach
resonance phenomena to tune the effective interaction between atoms. This tun-
ability arises from the coupling of free unbound atoms to a molecular state in which
the atoms are tightly bound. The closer this molecular level lies with respect to the
energy of two free atoms, the stronger the interaction between them. In the example
on the left, the two free atoms are both “spin up”, whereas the molecular state is a
“singlet”, in which the atoms have opposite spin, adding up to zero total magnetic
moment. Thus, a magnetic field shifts the energies of two free atoms relative to the
molecular state and thereby controls the interatomic interaction strength.
The interaction between two atoms can be described by the scattering length,
shown right as a function of magnetic field close to a Feshbach resonance. On the side
where the scattering length is positive, the molecular energy level is lower in energy
than the energy of two unbound atoms. The molecular state is thus “real” and stable,
and atoms tend to form molecules. If those atoms are fermions, the resulting molecule
is a boson. A gas of these molecules can thus undergo Bose-Einstein condensation
(BEC). This side of the resonance is therefore called “BEC-side”. On the side of the
resonance where the scattering length is negative, isolated molecules are unstable.
Nevertheless, when surrounded by the medium of others, two fermions can still form
a loosely bound pair, whose size can become comparable to or even larger than the
average distance between particles. A Bose-Einstein condensate of these fragile pairs
is called a “BCS-state”, after Bardeen, Cooper and Schrieffer. This is what occurs in
superconductors, in which current flows without resistance thanks to a condensate of
electron pairs (“Cooper pairs”).

14.3 The Born approximation

The partial wave expansion is tailored to the consideration of low-energy scat-
tering processes. At higher energies, when many partial waves contribute,
the expansion is not very convenient and it is helpful to develop a different
methodology. By developing a general expansion of the scattering wavefunc-
tion, ψk (r), in terms of the Green function of the scattering potential one may
show that,
, !
1 eik|r−r |
ψk (r) = eik·r − d3 r $ U (r$ )ψk (r$ ) . (14.3)
4π |r − r$ |

Here the subscript k reminds us that the solution is for a particular incom-
ing plane wave. This integral representation of the scattering wavefunction,
known as the Lippmann-Schwinger equation, provides a more useful basis to
address situations where the energy of the incoming particles is large and the
scattering potential is weak. The elements of the derivation of this equation
are summarised in the info box below:

$ Info. Lippmann-Schwinger equation: For the time-independent Schrödinger

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14.3. THE BORN APPROXIMATION 163

equation (∇2 + k 2 )ψ(r) = U (r)ψ(r), the general solution can be written formally as
,
ψ(r) = φ(r) + d3 r# G0 (r, r# )U (r# )ψ(r# ) ,

where φ(r) is a solution of the homogeneous (free particle) Schrödinger equation,

(∇2 + k 2 )φ(r) = 0, and G0 (r, r# ) is a Green function of the Laplace operator, (∇2 +
k 2 )G0 (r, r# ) = δ 3 (r − r# ). From the asymptotic behaviour of the boundary condition,
it is evident that φ(r) = eik·r . In the Fourier basis, the Green function is diagonal
and given by G0 (k, k# ) = (2π)3 δ 3 (k − k# ) k12 . Transformed back into real space, we
have
!
1 eik|r−r |
G0 (r, r# ) = − .
4π |r − r# |

Substituted back into the expression for the scattering wavefunction, we obtain the
Lippmann-Schwinger equation (14.3).

In the far-field region, |r − r$ | $ r − r̂ · r$ + · · ·, i.e.

!
eik|r−r | eikr −ik! ·r!
$ e ,
|r − r$ | r

where the vector k$ = kêr is oriented along the direction of the scattered
particle. We therefore find that the scattering wavefunction ψk (r) = eik·r +
ikr
f (θ, φ) e r can be expressed in integral form, with the scattering amplitude
given by
,
1 1 !
f (θ, φ) = − (φk! |U |ψk ) ≡ − d3 r$ e−ik ·r U (r$ )ψk (r$ ) . (14.4)
4π 4π

The corresponding differential cross-section can then be expressed as

dσ m2
= |f |2 = |Tk,k! |2 ,
dΩ (2π)2 !4

where, cast in terms of the original scattering potential, V (r) = !2 U (r)/2m,

Tk,k! = (φk! |V |ψk ) denotes the transition matrix element.
Eq. (14.3) provides a natural means to expand the scattering wavefunction
in powers of the interaction potential. At zeroth order in V , the scattering
(0)
wavefunction is specified by the unperturbed incident plane wave, φk (r) =
φk (r). Using this approximation, Eq. (14.3) leads to the first order correction,
,
(1) (0)
ψk (r) = φk (r) + d3 r$ G0 (r, r$ )U (r$ )ψk (r$ ) .

From this equation, we can use (14.3) to obtain the next term in the series,
,
(2) (1)
ψk (r) = φk (r) + d3 r$ G0 (r, r$ )U (r$ )ψk (r$ ) ,

and so on, i.e.

1
f =− (φk! |U + U G0 U + U G0 U G0 U + · · · |φk ) .
4π
Physically, an incoming particle undergoes a sequence of multiple scattering
events from the potential (see schematic on the right). This series expansion is

Advanced Quantum Physics

14.4. INFO: SCATTERING OF IDENTICAL PARTICLES 164

known as the Born series, and the leading term in known as the first Born
approximation to the scattering amplitude,

1
fBorn = − (φk! |U |φk ) . (14.5)
4π

Setting ∆ = k − k$ , where !∆ denotes the momentum transfer, the Born

scattering amplitude for a central potential is given by (exercise)
, , ∞
1 sin(∆r)
fBorn (∆) = − 3
d re i∆·r
U (r) = − rdr U (r) ,
4π 0 ∆

where, noting that |k$ | = |k|, ∆ = 2k sin(θ/2).

Coulomb scattering: Due to the long range nature of the Coulomb
scattering potential, the boundary condition on the scattering wavefunction
does not apply. We can, however, address the problem by working with the
−r/α
screened (Yukawa) potential, U (r) = U0 e r , and taking α → ∞. For this
potential, one may show that (exercise) fBorn = −U0 /(α−2 + ∆2 ). Therefore,
for α → ∞, we obtain

U02
σ(θ) = |f (θ)|2 = ,
16k 4 sin4 θ/2
which is just the Rutherford formula.

$ Info. Previously, we have used time-dependent perturbation theory to develop

an expression for the transition rate between states. In the leading order of pertur-
bation theory, we found that the transition rate between states and i and f induced
by a potential V is given by Fermi’s Golden rule,
2π
Γi→f = |(f|V |i)|2 δ(E − (Ef − Ei )) .
!
In a three-dimensional scattering problem, we should consider the initial state as a
plane wave state of wavevector k and the final state as the continuum of states with
wavevectors k# . In this case, the total transition (or scattering) rate into a fixed solid
angle, dΩ, is given by
$ 2π 2π #
Γk→k! = |(k# |V |k)|2 δ(E − (Ek! − Ek )) = |(k |V |k)|2 g(E) ,
!
! !
k ∈dΩ

where g(E) = dE dn
denotes the density of states and both states |k) and |k# ) have
2
energy E = !2 k 2 /2m = !2 k # /2m – they are said to be “on-shell”. As a result, we
k2 dΩ m
obtain the density of states g(E) = dn
dk dE = (2π/L)3 !2 k while the incident flux per
dk

unit volume is given by !k/mL3 . As a result, we obtain the scattering cross-section,

Γk→k!
dΩ = !k/mL3
dσ

dσ 1 2mV
= |(k# | 2 |k)|2 .
dΩ (4π)2 !
We can therefore recognize that Fermi’s Golden rule is equivalent to the first
order Born approximation.

14.4 Info: Scattering of identical particles

Until now, we have assumed that the particles involved in the scattering process,
the incoming particle and the target, are distinguishable. However, very often we
are interested in the scattering of identical quantum particles. In such cases, we

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14.5. SCATTERING BY AN ATOMIC LATTICE 165

have to consider the influence of quantum statistics on the scattering process. As a

preliminary exercise, consider the classical picture of scattering between two identical
positively charged particles, e.g. α-particles viewed in the center of mass frame. If an
outgoing α particle is detected at an angle θ to the path of the ingoing α-particle, it
could be (a) deflected through an angle θ, or (b) deflected through π − θ. Classically,
we could tell which one it was by watching the collision as it happened, and keeping
track. However, in a quantum mechanical scattering process, we cannot keep track of
the particles unless we bombard them with photons having wavelength substantially
less than the distance of closest approach. This is just like detecting an electron at a
particular place when there are two electrons in a one dimensional box: the probability
amplitude for finding an α particle coming out at angle θ to the ingoing direction of
one of them is the sum of the amplitudes (not the sum of the probabilities!) for
scattering through θ and π − θ.
Writing the asymptotic scattering wavefunction in the standard form for scatter-
ikr
ing from a fixed target, ψ(r) ≈ eikz + f (θ) e r , the two-particle wavefunction in the
center of mass frame, in terms of the relative coordinate, is given by symmetrizing:
eikr
ψ(r) ≈ eikz + e−ikz + (f (θ) + f (π − θ)) .
r
How does the particle symmetry affect the actual scattering rate at an angle θ? If
the particles were distinguishable, the differential cross section would be ( dΩ
dσ
)dist. =
|f (θ)| + |f (π − θ)| , but quantum mechanically we must compute,
2 2

* +
dσ
= |f (θ) + f (π − θ)|2 .
dΩ indist.
This makes a big difference! For example, for scattering through 90o , where f (θ) =
f (π−θ), the quantum mechanical scattering rate is twice the classical (distinguishable)
prediction.
Furthermore, if we make the standard
-∞ expansion of the scattering amplitude f (θ)
in terms of partial waves, f (θ) = "=0 (2+ + 1)a" P" (cos θ), then
∞
$
f (θ) + f (π − θ) = (2+ + 1)a" (P" (cos θ) + P" (cos(π − θ))) .
l=0

Since P" (−x) = (−1)" P" (x), the scattering only takes place in even partial wave
states. This is the same thing as saying that the overall wavefunction of two identical
bosons is symmetric. So, if they are in an eigenstate of total angular momentum,
from P" (−x) = (−1)" P" (x) it has to be a state of even +.
For fermions in an antisymmetric spin state, such as proton-proton scattering with
the two proton spins forming a singlet, the spatial wavefunction is symmetric, and the
argument is the same as for the boson case above. For parallel spin protons, however,
the spatial wavefunction has to be antisymmetric, and the scattering amplitude will
then be f (θ) − f (π − θ). In this case there is zero scattering at 90o ! Note that for
(non-relativistic) equal mass particles, the scattering angle in the center of mass frame
is twice the scattering angle in the fixed target (lab) frame.

14.5 Scattering by an atomic lattice

Finally, to close this section, let us say a few words about scattering phenomena
in solid state systems. If we ignore spin degrees of freedom, so that we do not
have to worry whether an electron does or does not flip its spin during the
scattering process, then at low energies, the scattering amplitude of particles
from a crystal f (θ) becomes independent of angle (s-wave). In this case, the
solution of the Schrödinger equation by a single atom i located at a point Ri
has the asymptotic form,
eik|r−Ri |
ψ(r) = eik·(r−Ri ) + f .
|r − Ri |

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14.5. SCATTERING BY AN ATOMIC LATTICE 166

Now, since
* +1/2
. /1/2 2r · Ri
k|r − Ri | = k r − 2r · Ri +
2
R2i $ kr 1 − $ kr − kêr · Ri ,
r2

and kêr = k$ , we have

" ikr
#
−ikRi −i(k! −k)·Ri e
ψ(r) = e eik·r
+ fe .
r

As a result, we can deduce the effective scattering amplitude,

f (θ) = f e−i∆·Ri , ∆ = k$ − k .

If we consider scattering from a crystal lattice, we must sum over all atoms. X-ray diffraction pattern of a
In this case, the total differential scattering cross-section is given by quasi-crystal.
0 02
0 0
dσ 0 $ 0
0 −i∆·Ri 0
= 0f e 0 .
dΩ 0 0
Ri

In the case of a periodic crystal, the sum over atoms translates to the Bragg
condition,

dσ (2π)3
= |f |2 3 δ (3) (k$ − k − 2πn/L) ,
dΩ L
where L represents the size of the (cubic) lattice, and n denote a vector of
integers – the Miller indices of the Bragg planes. We therefore expect that
the differential cross-section is very small expect when k$ − k = 2πn/L. These
relations can be generalised straightforwardly to address more complicated
crystal structures.

Advanced Quantum Physics

Chapter 15

Relativistic Quantum
Mechanics

The aim of this chapter is to introduce and explore some of the simplest aspects
of relativistic quantum mechanics. Out of this analysis will emerge the Klein-
Gordon and Dirac equations, and the concept of quantum mechanical spin.
This introduction prepares the way for the construction of relativistic quantum
field theories, aspects touched upon in our study of the quantum mechanics
of the EM field. To prepare our discussion, we begin first with a survey of
the motivations to seek a relativistic formulation of quantum mechanics, and
some revision of the special theory of relativity.
Why study relativistic quantum mechanics? Firstly, there are many ex-
perimental phenomena which cannot be explained or understood within the
purely non-relativistic domain. Secondly, aesthetically and intellectually it
would be profoundly unsatisfactory if relativity and quantum mechanics could
not be united. Finally there are theoretical reasons why one would expect new
phenomena to appear at relativistic velocities.
When is a particle relativistic? Relativity impacts when the velocity ap-
proaches the speed of light, c or, more intrinsically, when its energy is large
compared to its rest mass energy, mc2 . For instance, protons in the accelera-
tor at CERN are accelerated to energies of 300GeV (1GeV= 109 eV) which is
considerably larger than their rest mass energy, 0.94 GeV. Electrons at LEP
are accelerated to even larger multiples of their energy (30GeV compared to
5 × 10−4 GeV for their rest mass energy). In fact we do not have to appeal to
such exotic machines to see relativistic effects – high resolution electron mi-
croscopes use relativistic electrons. More mundanely, photons have zero rest
mass and always travel at the speed of light – they are never non-relativistic.
What new phenomena occur? To mention a few:

! Particle production: One of the most striking new phenomena to

emerge is that of particle production – for example, the production of
electron-positron pairs by energetic γ-rays in matter. Obviously one
needs collisions involving energies of order twice the rest mass energy of
the electron to observe production.
Astrophysics presents us with several examples of pair production. Neu-
trinos have provided some of the most interesting data on the 1987 su-
pernova. They are believed to be massless, and hence inherently rela-
tivistic; moreover the method of their production is the annihilation of
electron-positron pairs in the hot plasma at the core of the supernova.
High temperatures, of the order of 1012 K are also inferred to exist in the
nuclei of some galaxies (i.e. kB T " 2mc2 ). Thus electrons and positrons

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 168

Figure 15.1: Anderson’s cloud chamber picture of cosmic radiation from 1932 show-
ing for the first time the existence of the positron. A cloud chamber contains a gas
supersaturated with water vapour (left). In the presence of a charged particle (such
as the positron), the water vapour condenses into droplets – these droplets mark out
the path of the particle. In the picture a charged particle is seen entering from the
bottom at high energy. It then looses some of the energy in passing through the 6 mm
thick lead plate in the middle. The cloud chamber is placed in a magnetic field and
from the curvature of the track one can deduce that it is a positively charged particle.
From the energy loss in the lead and the length of the tracks after passing though the
lead, an upper limit of the mass of the particle can be made. In this case Anderson
deduces that the mass is less that two times the mass of the electron. Carl Anderson
(right) won the 1936 Nobel Prize for Physics for this discovery. (The cloud chamber
track is taken from C. D. Anderson, The positive electron, Phys. Rev. 43, 491 (1933).

are produced in thermal equilibrium like photons in a black-body cavity.

Again a relativistic analysis is required.

! Vacuum instability: Neglecting relativistic effects, we have shown that

the binding energy of the innermost electronic state of a nucleus of charge
Z is given by,
! 2 "2
Ze m
E=− .
4π$0 2!2
If such a nucleus is created without electrons around it, a peculiar phe-
nomenon occurs if |E| > 2mc2 . In that case, the total change in energy
of producing an electron-positron pair, subsequently binding the elec-
tron in the lowest state and letting the positron escape to infinity (it
is repelled by the nucleus), is negative. There is an instability! The
attractive electrostatic energy of binding the electron pays the price of
producing the pair. Nuclei with very high atomic mass spontaneously
“screen” themselves by polarising the vacuum via electron-positron pro-
duction until the they lower their charge below a critical value Zc . This
implies that objects with a charge greater than Zc are unobservable due
to screening.

! Info. An estimate based on the non-relativistic formula above gives Zc $

270. Taking into account relativistic effects, the result is renormalised down-
wards to 137, while taking into account the finite size of the nucleus one finally
obtains Zc ∼ 165. Of course, no such nuclei exist in nature, but they can be
manufactured, fleetingly, in uranium ion collisions where Z = 2 × 92 = 184.
Indeed, the production rate of positrons escaping from the nucleus is seen to
increase dramatically as the total Z of the pair of ions passes 160.

! Spin: Finally, while the phenomenon of electron spin has to be grafted

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 169

artificially onto the non-relativistic Schrödinger equation, it emerges nat-

urally from a relativistic treatment of quantum mechanics.
When do we expect relativity to intrude into quantum mechanics? Accord-
ing to the uncertainty relation, ∆x∆p ≥ !/2, the length scale at which the
kinetic energy is comparable to the rest mass energy is set by the Compton
wavelength
h
∆x ≥ ≡ λc .
mc
We may expect relativistic effects to be important if we examine the motion
of particles on length scales which are less than λc . Note that for particles of
zero mass, λc = ∞! Thus for photons, and neutrinos, relativity intrudes at
any length scale.
What is the relativistic analogue of the Schrödinger equation? Non-relativistic
quantum mechanics is based on the time-dependent Schrödinger equation
Ĥψ = i!∂t ψ, where the wavefunction ψ contains all information about a given
system. In particular, |ψ(x, t)|2 represents the probability density to observe a
particle at position x and time t. Our aim will be to seek a relativistic version
of this equation which has an analogous form. The first goal, therefore, is to
find the relativistic Hamiltonian. To do so, we first need to revise results from
Einstein’s theory of special relativity:

! Info. Lorentz Transformations and the Lorentz Group: In the special

theory of relativity, a coordinate in space-time is specified by a 4-vector. A con-
travariant 4-vector x = (xµ ) ≡ (x0 , x1 , x2 , x3 ) ≡ (ct, x) is transformed into the
covariant 4-vector xµ = gµν xν by the Minkowskii metric
 
1
 −1 
(gµν ) =  , gµν gνλ = δµλ ,
−1
−1
Here, by convention, summation is assumed over repeated indicies. Indeed, sum-
mation covention will be assumed throughout this chapter. The scalar product of
4-vectors is defined by
x · y = xµ y µ = xµ y ν gµν = xµ yµ .
The Lorentz group consists of linear Lorentz transformations, Λ, preserving x·y,
µ
i.e. for xµ )→ x! = Λµν xν , we have the condition

gµν Λµα Λνβ = gαβ . (15.1)

Specifically, a Lorentz transformation along the x1 direction can be expressed in the

form
 
γ −γv/c
 −γv/c γ 
Λµν =  
1 0
0 1
where γ = (1 − v 2 /c2 )−1/2 .1 With this definition, the Lorentz group splits up into
four components. Every Lorentz transformation maps time-like vectors (x2 > 0) into
1
Equivalently the Lorentz transformation can be represented in the form
0 1
0 −1
B −1 0 C
Λ = exp[ωK1 ], [K1 ]µν = B
@
C,
0 0A
0 0
where ω = tanh−1 (v/c) is known as the rapidity, and K1 is the generator of velocity
transformations along the x1 -axis.

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15.1. KLEIN-GORDON EQUATION 170

time-like vectors. Time-like vectors can be divided into those pointing forwards in
time (x0 > 0) and those pointing backwards (x0 < 0). Lorentz transformations do
not always map forward time-like vectors into forward time-like vectors; indeed Λ
does so if and only if Λ00 > 0. Such transformations are called orthochronous.
(Since Λµ0 Λµ0 = 1, (Λ00 )2 − (Λj0 )2 = 1, and so Λ00 += 0.) Thus the group splits
into two according to whether Λ00 > 0 or Λ00 < 0. Each of these two components
may be subdivided into two by considering those Λ for which det Λ = ±1. Those
transformations Λ for which det Λ = 1 are called proper.
Thus the subgroup of the Lorentz group for which det Λ = 1 and Λ00 > 0 is
called the proper orthochronous Lorentz group, sometimes denoted by L↑+ . It
contains neither the time-reversal nor parity transformation,
   
−1 1
 1   −1 
T = , P = . (15.2)
1 −1
1 −1
We shall call it the Lorentz group for short and specify when we are including T or P .
In particular, L↑+ , L↑ = L↑+ ∪ L↑− (the orthochronous Lorentz group), L+ = L↑+ ∪ L↓+
(the proper Lorentz group), and L0 = L↑+ ∪ L↓− are subgroups, while L↓− = P L↑+ ,
L↑− = T L↑+ and L↓+ = T P L↑+ are not.
Special relativity requires that theories should be invariant under Lorentz trans-
formations xµ )−→ Λµν xν , and, more generally, Poincaré transformations xµ →
Λµν xν + aµ . The proper orthochronous Lorentz transformations can be reached con-
tinuously from identity.2 Loosely speaking, we can form them by putting together
infinitesimal Lorentz transformations Λµν = δ µν + ω µν , where the elements of ω µν - 1.
Applying the identity gαβ = Λµα Λµβ = gαβ + ωαβ + ωβα + O(ω 2 ), we obtain the
relation ωαβ = −ωβα . ωαβ has six independent components: L↑+ is a six-dimensional
(Lie) group, i.e. it has six independent generators: three rotations and three boosts.
Finally, according to the definition of the 4-vectors, the covariant and contravari-
ant derivative are respectively defined by ∂µ = ∂x∂ µ = ( 1c ∂t ∂
, ∇), ∂ µ = ∂x∂ µ =
( 1c ∂t
∂
, −∇). Applying the scalar product to the derivative we obtain the d’Alembertian
∂2
operator (sometimes denoted as !), ∂ 2 = ∂µ ∂ µ = c12 ∂t 2 − ∇ .
2

15.1 Klein-Gordon equation

Historically, the first attempt to construct a relativistic version of the Schrödinger
equation began by applying the familiar quantization rules to the relativistic Oskar Benjamin Klein 1894-
energy-momentum invariant. In non-relativistic quantum mechanics the cor- 1977
respondence principle dictates that the momentum operator is associated with A Swedish theo-
retical physicist,
the spatial gradient, p̂ = −i!∇, and the energy operator with the time deriva- Klein is credited
tive, Ê = i!∂t . Since (pµ ≡ (E/c, p) transforms like a 4-vector under Lorentz for inventing
the idea, part
transformations, the operator p̂µ = i!∂ µ is relativistically covariant. of Kaluza-Klein
Non-relativistically, the Schrödinger equation is obtained by quantizing theory, that extra
the classical Hamiltonian. To obtain a relativistic version of this equation, dimensions may
be physically real
one might apply the quantization relation to the dispersion relation obtained but curled up
from the energy-momentum invariant p2 = (E/c)2 − p2 = (mc)2 , i.e. and very small, an idea essential to
string theory/M-theory.
) 2 4 *
2 2 1/2
+ 2 4 ,
2 2 2 1/2
E(p) = + m c + p c ⇒ i!∂t ψ = m c − ! c ∇ ψ
where m denotes the rest mass of the particle. However, this proposal poses
a dilemma: how can one make sense of the square root of an operator? Inter-
preting the square root as the Taylor expansion,
!2 ∇2 !4 (∇2 )2
i!∂t = mc2 ψ − ψ− ψ + ···
2m 8m3 c2
2
They are said to form the path component of the identity.

Advanced Quantum Physics

15.1. KLEIN-GORDON EQUATION 171

we find that an infinite number of boundary conditions are required to specify

the time evolution of ψ.3 It is this effective “non-locality” together with the
asymmetry (with respect to space and time) that suggests this equation may
be a poor starting point.
A second approach, and one which circumvents these difficulties, is to apply
the quantization procedure directly to the energy-momentum invariant:
) *
E 2 = p2 c2 + m2 c4 , −!2 ∂t2 ψ = −!2 c2 ∇2 + m2 c4 ψ.

Recast in the Lorentz invariant form of the d’Alembertian operator, we obtain

the Klein-Gordon equation

) *
∂ 2 + kc2 ψ = 0 , (15.3)

where kc = 2π/λc = mc/!. Thus, at the expense of keeping terms of second

order in the time derivative, we have obtained a local and manifestly covariant
equation. However, invariance of ψ under global spatial rotations implies that,
if applicable at all, the Klein-Gordon equation is limited to the consideration of
spin-zero particles. Moreover, if ψ is the wavefunction, can |ψ|2 be interpreted
as a probability density?
To associate |ψ|2 with the probability density, we can draw intuition from
the consideration of the non-relativistic Schrödinger equation. Applying the
identity ψ ∗ (i!∂t ψ + !2m
2 ∇2
ψ) = 0, together with the complex conjugate of this
equation, we obtain
!
∂t |ψ|2 − i ∇ · (ψ ∗ ∇ψ − ψ∇ψ ∗ ) = 0 .
2m
Conservation of probability means that density ρ and current j must satisfy
the continuity relation, ∂t ρ + ∇ · j = 0, which states simply that the rate of
decrease of density in any volume element is equal to the net current flowing
out of that element. Thus, for the Schrödinger equation, we can consistently
!
define ρ = |ψ|2 , and j = −i 2m (ψ ∗ ∇ψ − ψ∇ψ ∗ ).
Applied to the Klein-Gordon equation (15.3), the same consideration im-
plies

!2 ∂t (ψ ∗ ∂t ψ − ψ∂t ψ ∗ ) − !2 c2 ∇ · (ψ ∗ ∇ψ − ψ∇ψ ∗ ) = 0 ,

from which we deduce the correspondence,

! !
ρ=i (ψ ∗ ∂t ψ − ψ∂t ψ ∗ ) , j = −i (ψ ∗ ∇ψ − ψ∇ψ ∗ ) .
2mc2 2m
The continuity equation associated with the conservation of probability can
be expressed covariantly in the form

∂µ j µ = 0 , (15.4)

where j µ = (ρc, j) is the 4-current. Thus, the Klein-Gordon density is the

time-like component of a 4-vector.
From this association it is possible to identify three aspects which (at least
initially) eliminate the Klein-Gordon equation as a wholey suitable candidate
for the relativistic version of the wave equation:
3
You may recognize that the leading correction to the free particle Schrödinger equation
is precisely the relativistic correction to the kinetic energy that we considered in chapter 9.

Advanced Quantum Physics

15.2. DIRAC EQUATION 172

! The first disturbing feature of the Klein-Gordon equation is that the

density ρ is not a positive definite quantity, so it can not represent a
probability. Indeed, this led to the rejection of the equation in the early
years of relativistic quantum mechanics, 1926 to 1934.

! Secondly, the Klein-Gordon equation is not first order in time; it is

necessary to specify ψ and ∂t ψ everywhere at t = 0 to solve for later
times. Thus, there is an extra constraint absent in the Schrödinger
formulation.

! Finally, the equation on which the Klein-Gordon equation is based,

E 2 = m2 c4 + p2 c2 , has both positive and negative solutions. In fact
the apparently unphysical negative energy solutions are the origin of the
preceding two problems. Paul A. M. Dirac 1902-1984
Dirac was born
To circumvent these difficulties one might consider dropping the negative on 8th August,
1902, at Bristol,
energy solutions altogether. For a free particle, whose energy is thereby con- England, his fa-
stant, we can simply supplement the Klein-Gordon equation with the condition ther being Swiss
p0 > 0. However, such a definition becomes inconsistent in the presence of and his mother
English. He was
local interactions, e.g. educated at the Merchant Venturer’s
Secondary School, Bristol, then went
) 2 * on to Bristol University. Here, he
∂ + kc2 ψ = F (ψ) self − interaction studied electrical engineering, obtain-
- .
2 ing the B.Sc. (Engineering) degree
(∂ + iqA/!c) + kc ψ = 0
2
interaction with EM field. in 1921. He then studied mathemat-
ics for two years at Bristol University,
The latter generate transitions between positive and negative energy states. later going on to St. John’s Col-
lege, Cambridge, as a research stu-
Thus, merely excluding the negative energy states does not solve the problem. dent in mathematics. He received his
Later we will see that the interpretation of ψ as a quantum field leads to a Ph.D. degree in 1926. The following
year he became a Fellow of St.John’s
resolution of the problems raised above. Historically, the intrinsic problems College and, in 1932, Lucasian Pro-
confronting the Klein-Gordon equation led Dirac to introduce another equa- fessor of Mathematics at Cambridge.
Dirac’s work was concerned with the
tion.4 However, as we will see, although the new formulation implied a positive mathematical and theoretical aspects
norm, it did not circumvent the need to interpret negative energy solutions. of quantum mechanics. He began
work on the new quantum mechan-
ics as soon as it was introduced by
Heisenberg in 1928 – independently
15.2 Dirac Equation producing a mathematical equivalent
which consisted essentially of a non-
Dirac attached great significance to the fact that Schrödinger’s equation of commutative algebra for calculating
atomic properties – and wrote a series
motion was first order in the time derivative. If this holds true in relativistic of papers on the subject, leading up
quantum mechanics, it must also be linear in ∂. On the other hand, for to his relativistic theory of the elec-
tron (1928) and the theory of holes
free particles, the equation must imply p̂2 = (mc)2 , i.e. the wave equation (1930). This latter theory required
must be consistent with the Klein-Gordon equation (15.3). At the expense of the existence of a positive particle
introducing vector wavefunctions, Dirac’s approach was to try to factorise this having the same mass and charge as
the known (negative) electron. This,
equation: the positron was discovered experi-
mentally at a later date (1932) by
C. D. Anderson, while its existence
was likewise proved by Blackett and
(γ µ p̂µ − m) ψ = 0 . (15.5) Occhialini (1933) in the phenomena
of “pair production” and “annihila-
tion”. Dirac was made the 1933 No-
bel Laureate in Physics (with Erwin
(Following the usual convention we have, and will henceforth, adopt the short- Schrödinger) for the discovery of new
hand convention and set ! = c = 1.) For this equation to be admissible, the productive forms of atomic theory.
following conditions must be enforced:

! The components of ψ must satisfy the Klein-Gordon equation.

4
The original references are P. A. M. Dirac, The Quantum theory of the electron, Proc.
R. Soc. A117, 610 (1928); Quantum theory of the electron, Part II, Proc. R. Soc. A118,
351 (1928). Further historical insights can be obtained from Dirac’s book on Principles of
Quantum mechanics, 4th edition, Oxford University Press, 1982.

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15.2. DIRAC EQUATION 173

! There must exist a 4-vector current density which is conserved and whose
time-like component is a positive density.
! The components of ψ do not have to satisfy any auxiliary condition. At
any given time they are independent functions of x.
Beginning with the first of these requirements, by imposing the condition
[γ µ , p̂ν ] = γ µ p̂ν − p̂ν γ µ = 0, (and symmetrizing)
! "
1 ν µ
(γ p̂ν + m) (γ p̂µ − m) ψ =
ν µ
{γ , γ } p̂ν p̂µ − m ψ = 0 ,
2
2
the latter recovers the Klein-Gordon equation if we define the elements γ µ such
that they obey the anticommutation relation,5 {γ ν , γ µ } ≡ γ ν γ µ + γ µ γ ν = 2g µν
– thus γ µ , and therefore ψ, can not be scalar. Then, from the expansion of
Eq. (15.5), γ 0 (γ 0 p̂0 − γ · p̂ − m)ψ = i∂t ψ − γ 0 γ · p̂ψ − mγ 0 ψ = 0, the Dirac
equation can be brought to the form

i∂t ψ = Ĥψ, Ĥ = α · p̂ + βm , (15.6)

where the elements of the vector α = γ 0 γ and β = γ 0 obey the commutation

relations,
{αi , αj } = 2δij , β 2 = 1, {αi , β} = 0 . (15.7)
Ĥ is Hermitian if, and only if, α† = α, and β † = β. Expressed in terms of
†
γ, this requirement translates to the condition (γ 0 γ)† ≡ γ † γ 0 = γ 0 γ, and
†
γ 0 = γ 0 . Altogether, we thus obtain the defining properties of Dirac’s γ
matrices,

γ µ† = γ 0 γ µ γ 0 , {γ µ , γ ν } = 2g µν . (15.8)

Given that space-time is four-dimensional, the matrices γ must have dimen-

sion of at least 4 × 4, which means that ψ has at least four components. It is
not, however, a 4-vector; it does not transform like xµ under Lorentz trans-
formations. It is called a spinor, or more correctly, a bispinor with special
Lorentz transformations which we will shall discuss presently.

! Info. An explicit representation of the γ matrices which most easily captures

the non-relativistic limit is the following,
! " ! "
I2 0 0 σ
γ0 = , γ= , (15.9)
0 −I2 −σ 0
where σ denote the familiar 2 × 2 Pauli spin matrices which satisfy the relations,
σi σj = δij + i$ijk σk , σ † = σ. The latter is known in the literature as the Dirac-
Pauli representation. We will adopt the particular representation,
! " ! " ! "
0 1 0 −i 1 0
σ1 = , σ2 = , σ3 = .
1 0 i 0 0 −1
Note that with this definition, the matrices α and β take the form,
! " ! "
0 σ I2 0
α= , β= .
σ 0 0 −I2

5
Note that, in some of the literature, you will see the convention [ , ]+ for the anticom-
mutator.

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15.2. DIRAC EQUATION 174

15.2.1 Density and Current

Turning to the second of the requirements placed on the Dirac equation, we
now seek the probability density ρ = j 0 . Since ψ is a complex spinor, ρ has
to be of the form ψ † M ψ in order to be real and positive. Applying hermitian
conjugation to the Dirac equation, we obtain
µ←
−
[(γ µ p̂µ − m)ψ]† = ψ † (−iγ † ∂ µ − m) = 0 ,
←
−
where ψ † ∂ µ ≡ (∂µ ψ)† . Making use of (15.8), and defining ψ̄ ≡ ψ † γ 0 , the
←−
Dirac equation takes the form ψ̄(i + ∂ + m) = 0, where we have introduced
the Feynman ‘slash’ notation + a ≡ aµ γ µ . Combined with Eq. (15.5) (i.e.
−
→
(i + ∂ − m)ψ = 0), we obtain
/ 0 ) *
←− − →
ψ̄ + ∂ + + ∂ ψ = ∂µ ψ̄γ µ ψ = 0 .

From this result and the continuity relation (15.4) we can identify

j µ = ψ̄γ µ ψ , (15.10)

(or, equivalently, (ρ, j) = (ψ † ψ, ψ † αψ)) as the 4-current. In particular, the

density ρ = j 0 = ψ † ψ is, as required, positive definite.

15.2.2 Relativistic Covariance

To complete our derivation, we must verify that the Dirac equation remains
invariant under Lorentz transformations. More precisely, if a wavefunction
ψ(x) obeys the Dirac equation in one frame, its counterpart ψ $ (x$ ) in a Lorentz
transformed frame x$ = Λx, must obey the Dirac equation,
) µ $ *
iγ ∂µ − m ψ $ (x$ ) = 0 . (15.11)

In order that an observer in the second frame can reconstruct ψ $ from ψ there
must exist a local transformation between the wavefunctions. Taking this
relation to be linear, we therefore must have,

ψ $ (x$ ) = S(Λ)ψ(x) ,

where S(Λ) represents a non-singular 4 × 4 matrix. Now, using the identity,

∂xν ∂
∂µ$ ≡ ∂x∂" µ = ∂x" µ ∂xν = (Λ
−1 )ν ∂ = (Λ−1 )ν ∂ , the Dirac equation (15.11)
µ ∂xν µ ν
in the transformed frame takes the form,
) µ −1 ν *
iγ (Λ ) µ ∂ν − m S(Λ)ψ(x) = 0 .

The latter is compatible with the Dirac equation in the original frame if

S(Λ)γ ν S −1 (Λ) = γ µ (Λ−1 )νµ . (15.12)

To define an explicit form for S(Λ) we must now draw upon some of the
defining properties of the Lorentz group discussed earlier. For an infinitesi-
mal proper Lorentz transformation we have Λνµ = g νµ + ω νµ and (Λ−1 )νµ =
g νµ − ω νµ + · · ·, where the matrix ωµν is antisymmetric and g νµ ≡ δ νµ . Corre-
spondingly, by Taylor expansion in ω, we can define
i i
S(Λ) = I − Σµν ω µν + · · · , S −1 (Λ) = I + Σµν ω µν + · · · ,
4 4

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15.2. DIRAC EQUATION 175

where the matrices Σµν are also antisymmetric in µν. To first order in ω,
Eq. (15.12) yields (a somewhat unrewarding exercise!)
) *
[γ ν , Σαβ ] = 2i g να γβ − g νβ γα . (15.13)

The latter is satisfied by the set of matrices (another exercise!)6

i
Σαβ = [γα , γβ ] . (15.14)
2

In summary, if ψ(x) obeys the Dirac equation in one frame, the wavefunction
can be obtained in the Lorentz transformed frame by applying the transforma-
tion ψ $ (x$ ) = S(Λ)ψ(Λ−1 x$ ). Let us now consider the physical consequences
of this Lorentz covariance.

15.2.3 Angular momentum and spin

To explore the physical manifestations of Lorentz covariance, it is instructive
to consider the class of spatial rotations. For an anticlockwise spatial rotation
by an infinitesimal angle θ about a fixed axis n, x )→ x$ = x − θx × n. In
terms of the “Lorentz transformation”, Λ, one has

x$i = [Λx]i ≡ xi − ωij xj

where ωij = $ijk nk θ, and the remaining elements Λµ0 = Λ0µ = 0. Applied to
the argument of the wavefunction we obtain a familiar result,7

ψ(x) = ψ(Λ−1 x$ ) = ψ(x$0 , x$ + x$ × nθ) = (1 − θn · x$ × ∇ + · · ·)ψ(x$ )

= (1 − iθn · L̂ + · · ·)ψ(x$ ),

where L̂ = x̂ × p̂ represents the non-relativistic angular momentum operator.

Formally, the angular momentum operators represent the generators of spatial
rotations.8
However, we have seen above that Lorentz covariance demands that the
transformed wavefunction be multiplied by S(Λ). Using the definition of ωij
above, one finds that
i
S(Λ) ≡ S(I + ω) = I − $ijk nk Σij θ + · · ·
4
Then drawing on the Dirac/Pauli representation,
1! " ! "2
i i 0 σi 0 σj i
Σij = [γi , γj ] = , = − [σi , σj ] ⊗ I2 = $ijk σk ⊗ I2 ,
2 2 −σ i 0 −σ j 0 2
one obtains
! "
1 σ 0
S(Λ) = I − in · Sθ + · · · , S= .
2 0 σ

Combining both contributions, we thus obtain

ψ $ (x$ ) = S(Λ)ψ(Λ−1 x$ ) = (1 − iθn · Ĵ + · · ·)ψ(x$ ) ,

6
Since finite transformations are of the form S(Λ) = exp[−(i/4)Σαβ ω αβ ], one may show
that S(Λ) is unitary for spatial rotations, while it is Hermitian for Lorentz boosts.
7
Recall that spatial rotataions are generated by the unitary operator, Û (θ) = exp(−iθn ·
L̂).
8
For finite transformations, the generator takes the form exp[−iθn · L̂].

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15.3. FREE PARTICLE SOLUTION OF THE DIRAC EQUATION 176

where Ĵ = L̂ + S can be identified as a total effective angular momentum of

the particle being made up of the orbital component, together with an intrin-
sic contribution known as spin. The latter is characterised by the defining
condition:

1
[Si , Sj ] = i$ijk Sk , (Si )2 = for each i . (15.15)
4

Therefore, in contrast to non-relativistic quantum mechanics, the concept of

spin does not need to be grafted onto the Schrödinger equation, but emerges
naturally from the fundamental invariance of the Dirac equation under Lorentz
transformations. As a corollary, we can say that the Dirac equation is a
relativistic wave equation for particles of spin 1/2.

15.2.4 Parity
So far, our discussion of the covariance properties of the Dirac equation have
only dealt with the subgroup of proper orthochronous Lorentz transformations,
L↑+ – i.e. those that can be reached from Λ = I by a sequence of infinites-
imal transformations. Taking the parity operation into account, relativistic
covariance demands

S −1 (P )γ 0 S(P ) = γ 0 , S −1 (P )γ i S(P ) = −γ i .

This is achieved if S(P ) = γ 0 eiφ , where φ denotes some arbitrary phase.

Taking into account the fact that P 2 = I, φ = 0 or π, and we find

ψ $ (x$ ) = S(P )ψ(x) = ηγ 0 ψ(P −1 x$ ) = ηγ 0 ψ(ct$ , −x$ ) , (15.16)

where η = ±1 represents the intrinsic parity of the particle.

15.3 Free Particle Solution of the Dirac Equation

Having laid the foundation we will now apply the Dirac equation to the prob-
lem of a free relativistic quantum particle. For a free particle, the plane wave

ψ(x) = exp[−ip · x]u(p) ,

3
with energy E ≡ p0 = ± p2 + m2 will be a solution of the Dirac equation
if the components of the spinor u(p) are chosen to satisfy the equation (+ p −
m)u(p) = 0. Evidently, as with the Klein-Gordon equation, we see that the
Dirac equation therefore admits negative as well as positive energy solutions!
Soon, having attached a physical significance to the former, we will see that
it is convenient to reverse the sign of p for the negative energy solutions.
However, for now, let us continue without worrying about the dilemma posed
by the negative energy states.
In the Dirac-Pauli block representation,
! 0 "
p − m −σ · p
γ pµ − m =
µ
.
σ · p −p0 − m

Thus, defining the spin elements u(p) = (ξ, η), where ξ and η represent two-
component spinors, we find the conditions, (p0 − m)ξ = σ · p η and σ · p ξ =

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15.3. FREE PARTICLE SOLUTION OF THE DIRAC EQUATION 177

(p0 + m)η. With (p0 )2 = p2 + m2 , these equations are consistent if η = pσ ·p

0 +m ξ.
We therefore obtain the bispinor solution
 
χ(r)
u(r) (p) = N (p)  σ · p (r)  ,
χ
p0 + m
where χ(r) represents any pair of orthogonal two-component vectors, and N (p)
is the normalisation.
Concerning the choice of χ(r) , in many situations, the most convenient basis
is the eigenbasis of helicity – eigenstates of the component of spin resolved
in the direction of motion,
p (±) σ p (±) 1
S· χ ≡ · χ = ± χ(±) ,
|p| 2 |p| 2
e.g., for p = p3 ê3 , χ(+) = (1, 0) and χ(−) = (0, 1). Then, for the positive
energy states, the two spinor plane wave solutions can be written in the form
 
χ(±)
ψp(±) (x) = N (p)e−ip·x  |p|

(±)
± 0 χ
p +m
Thus, according to the discussion above, the Dirac equation for a free particle
admits four solutions, two states with positive energy, and two with negative.

15.3.1 Klein paradox: anti-particles

While the Dirac equation has been shown to have positive definite density,
as with the Klein-Gordon equation, it still exhibits negative energy states!
To make sense of these states it is illuminating to consider the scattering
of a plane wave from a potential step. To be precise, consider a beam of
relativistic particles with unit amplitude, energy E, momentum pê3 , and spin
↑ (i.e. χ = (1, 0)), incident upon a potential V (x) = V θ(x3 ) (see figure).
At the potential barrier, spin is conserved, while a component of the beam
with amplitude r is reflected (with energy E and momentum −pê3 ), and a
component t is transmitted with energy E $ = E − V and momentum p$ ê3 .
According to the energy-momentum invariant, conservation of energy across
the interface dictates that E 2 = p2 + m2 and E $ 2 = p$2 + m2 .
Being first order, the boundary conditions on the Dirac equation require
only continuity of ψ (cf. the Schrödinger equation). Therefore, matching ψ at
the step, we obtain the relations
     
1 1 1
 0     
 p  + r  0p  = t  p0"  ,
  −   " 
E+m E+m E +m
0 0 0
p p" p" (E+m)
from which we find 1 +r = t, and p0 +m
(1 − r) = p"0 +m
t. Setting ζ = p (E " +m) ,
these equations lead to
2 1+r 1 1−ζ
t= , = , r= .
1+ζ 1−r ζ 1+ζ
To interpret these solutions, let us consider the current associated with
the reflected and transmitted components. Making use of the equation for the
current density, j = ψ † αψ, and using the Dirac/Pauli representation wherein
! "! " ! "
I2 σ3 σ3
α3 = γ0 γ3 = = ,
−I2 −σ3 σ3

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15.3. FREE PARTICLE SOLUTION OF THE DIRAC EQUATION 178

the current along ê3 -direction is given by

! "
σ3
j3 = ψ † ψ, j1 = j2 = 0 .
σ3

Therefore, up to an overall constant of normalisation, the current densities are

given by

(i) 2p (t) 2(p$ + p$∗ ) 2 (r) 2p

j3 = , j3 = |t| , j3 = − |r|2 .
p0 +m p$0 + m p0 + m
From these relations we obtain
(t)
j3 (p$ + p$∗ ) p0 + m 4 1
= |t|2 = (ζ + ζ ∗ )
(i)
j3 2p p$0 + m |1 + ζ|2 2
(r) 4 4
j3 4 1 − ζ 42
= −|r| = − 44
2 4
(i)
j3 1+ζ4

from which current conservation can be confirmed:

(r) (t)
j3 |1 + ζ|2 − |1 − ζ|2 2(ζ + ζ ∗ ) j
1+ = = = 3(i) .
j3
(i) |1 + ζ| 2 |1 + ζ|2
j3
Interpreting these results, it is convenient to separate our consideration
into three distinct regimes of energy:
! E $ ≡ (E − V ) > m: In this case, from the Klein-Gordon condition (the
energy-momentum invariant) p$2 ≡ E $2 − m2 > 0, and (taking p$ > 0
– i.e. beam propagates to the right) ζ > 0 and real. From this result
(r) (i)
we find |j3 | < |j3 | – as expected, within this interval of energy, a
component of the beam is transmitted and the remainder is reflected
(cf. non-relativistic quantum mechanics).

! −m < E $ < m: In this case p$2 ≡ E $2 − m2 < 0 and p$ is purely

imaginary. From this result it follows that ζ is also pure imaginary and
(r) (i)
|j3 | = |j3 |. In this regime the under barrier solutions are evanescent
and quickly decay to the right of the barrier. All of the beam is reflected
(cf. non-relativistic quantum mechanics).

! E $ < −m: Finally, in this case p$2 ≡ E $2 −m2 > 0 and, depending on the
(r) (i)
sign of p$ , j3 can be greater or less than j3 . But the solution has the
" "
form e−i(p x−E t) . Since we presume the beam to be propagating to the
right, we require E $ < 0 and p$ > 0. From this result it follows that ζ < 0
(r) (i)
and we are drawn to the surprising conclusion that |j3 | > |j3 | – more
current is reflected that is incident! Since we have already confirmed
(t)
current conservation, we can deduce that j3 < 0. It is as if a beam of
particles were incident from the right.
The resolution of this last seeming unphysical result, known as the Klein
paradox,9 in fact gives a natural interpretation of the negative energy solu-
tions that plague both the Dirac and Klein-Gordon equations: Dirac particles
are fermionic in nature. If we regard the vacuum as comprised of a filled Fermi
sea of negative energy states or antiparticles (of negative charge), the Klein
Paradox can be resolved as the stimulated emission of particle/antiparticle
9
Indeed one would reach the same conclusion were one to examine the Klein-Gordon
equation.

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15.3. FREE PARTICLE SOLUTION OF THE DIRAC EQUATION 179

Figure 15.2: The photograph shows a

small part of a complicated high energy
neutrino event produced in the Fermi-
lab bubble chamber filled with a neon
hydrogen mixture. A positron (red)
emerging from an electron-positron
pair, produced by a gamma ray, curves
round through about 180 degrees.
Then it seems to change charge: it be-
gins to curve in the opposite direction
(blue). What has happened is that the
positron has run head-on into a (more-
or-less from the point of view of particle
physics) stationary electron – transfer-
ring all its momentum. This tells us
that the mass of the positron equals the
mass of the electron.

pairs, the particles moving off towards x3 = −∞ and the antiparticles towards
x3 = ∞. What about energy conservation? One might worry that the energy
for these pairs is coming from nowhere. However, the electrostatic energy re-
covered by the antiparticle when its created is sufficient to outweigh the rest
mass energy of the particle and antiparticle pair (remember that a repulsive
potential for particles is attractive for antiparticles). Taking into account the
fact that the minimum energy to create a particle/antiparticle pair is twice
the rest mass energy 2 × m, the regime where stimulated emission is seen to
occur can be understood.
Negative energy states: With this conclusion, it is appropriate to revisit
the definition of the free particle plane wave
3 state. In particular, for energies
E < 0, it is more sensible to set p0 = + (p2 + m2 ), and redefine the plane
wave solution as ψ(x) = v(p)eip·x , where the spinor satisfies the condition
(+ p + m)v(p) = 0. Accordingly we find,
5 σ · p (r) 6
χ
v (p) = N (p) p0 + m
(r)
.
χ(r)

So, to conclude, two relativistic wave equations have been proposed. The
first of these, the Klein-Gordon equation was dismissed on the grounds that
it exhibited negative probability densities and negative energy states. By
contrast, the states of the Dirac equation were found to exhibit a positive
definite probability density, and the negative energy states were argued to
have a natural interpretation in terms of antiparticles: the vacuum state does
not correspond to all states unoccupied but to a state in which all the negative
energy states are occupied – the negative energy states are filled up by a Fermi
sea of negative energy Fermi particles. For electron degrees of freedom, if a
positive energy state is occupied we observe it as a (positive energy) electron
of charge q = −e. If a negative energy state is unoccupied we observe it as a
(positive energy) antiparticle of charge q = +e, a positron, the antiparticle
of the electron. If a very energetic electron interacts with the sea causing a
transition from a negative energy state to positive one (by communicating an
energy of at least 2m) this is observed as the production of a pair of particles,
an electron and a positron from the vacuum (pair production) (see Fig. 15.2).

However, the interpretation attached to the negative energy states provides

grounds to reconsider the status of the Klein-Gordon equation. Evidently, the

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15.4. QUANTIZATION OF RELATIVISTIC FIELDS 180

Dirac equation is not a relativistic wave equation for a single particle. If it

were, pair production would not appear. Instead, the interpretation above
forces us to consider the wavefunction of the Dirac equation as a quantum
field able to host any number of particles – cf. the continuum theory of the
quantum harmonic chain. In the next section, we will find that the consid-
eration of the wavefunction as a field revives the Klein-Gordon equation as a
theory of scalar (interger spin) particles.

15.4 Quantization of relativistic fields

15.4.1 Info: Scalar field: Klein-Gordon equation revisited
Previously, the Klein-Gordon equation was abandoned as a candidate for a relativis-
tic theory on the basis that (i) it admitted negative energy solutions, and (ii) that
the probability density associated with the wavefunction was not positive definite.
Yet, having associated the negative energy solutions of the Dirac equation with an-
tiparticles, and identified ψ as a quantum field, it is appropriate that we revisit the
Klein-Gordon equation and attempt to revive it as a theory of relativistic particles of
spin zero.
If φ were a classical field, the Klein-Gordon equation would represent the equation
of motion associated with the Lagrangian density (exercise)

1 1
L= ∂µ φ ∂ µ φ − m2 φ2 ,
2 2

(cf. our discussion of the low energy modes of the classical harmonic chain and the
Maxwell field of the waveguide in chapter 11). Defining the canonical momentum
π(x) = ∂φ̇ L(x) = φ̇(x) ≡ ∂0 φ(x), the corresponding Hamiltonian density takes the
form
1+ 2 ,
H = π φ̇ − L = π + (∇φ)2 + m2 φ2 .
2
Evidently, the Hamiltonian density is explicitly positive definite. Thus, the scalar
field is not plagued by the negative energy problem which beset the single-particle
theory. Similarly, the quantization of the classical field will lead to a theory in which
the states have positive energy.
Following on from our discussion of the harmonic chain in chapter 11, we are
already equipped to quantise the classical field theory. However, there we worked ex-
plicitly in the Schrödinger representation, in which the dynamics was contained within
the time-dependent wavefunction ψ(t), and the operators were time-independent. Al-
ternatively, one may implement quantum mechanics in a representation where the
time dependence is transferred to the operators instead of the wavefunction — the
Heisenberg representation. In this representation, the Schrödinger state vector ψS (t)
is related to the Heisenberg state vector ψH by the relation,

ψS (t) = e−iĤt ψH , ψH = ψS (0) .

Similarly, Schrödinger operators ÔS are related to the Heisenberg operators ÔH (t) by

ÔH (t) = eiĤt ÔS e−iĤt .

One can easily check that the matrix elements 3ψS! |ÔS |ψS 4 and 3ψH !
|ÔH |ψH 4 are
equivalent in the two representations, and which to use in non-relativistic quantum
mechanics is largely a matter of taste and convenience. However, in relativistic quan-
tum field theory, the Heisenberg representation is often preferable to the Schrödinger
representation. The main reason for this is that by using the former, the Lorentz
covariance of the field operators is made manifest.

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15.4. QUANTIZATION OF RELATIVISTIC FIELDS 181

In the Heisenberg representation, the quantisation of the fields is still enforced by

promoting the classical fields to operators, π )→ π̂ and φ )→ φ̂, but in this case, we
impose the equal time commutation relations,
- . - .
φ̂(x, t), π̂(x! , t) = iδ 3 (x − x! ), φ̂(x, t), φ̂(x! , t) = [π̂(x, t), π̂(x! , t)] = 0 ,

with π̂ = ∂0 φ̂. In doing so, the Hamiltonian density takes the form
1- 2 .
Ĥ = π̂ + (∇φ̂)2 + m2 φ̂2 .
2
To see the connection between the quantized field and particles we need to Fourier
transform the field operators to obtain the normal modes of the Hamiltonian,
7
d4 k
φ̂(x) = φ̂(k)e−ik·x .
(2π)4

However the form of the Fourier elements φ̂(k) is constrained by the following con-
ditions. Firstly to maintain Hermiticity of the field operator φ̂(x) we must choose
Fourier coefficients such that φ̂† (k) = φ̂(−k). Secondly, to ensure that the field op-
erator φ̂(x) obeys the Klein-Gordon equation,10 we require φ̂(k) ∼ 2πδ(k 2 − m2 ).
Taking these conditions together, we require
) *
φ̂(k) = 2πδ(k 2 − m2 ) θ(k 0 )a(k) + θ(−k 0 )a† (−k) ,
√
where k 0 ≡ ωk ≡ + k2 + m2 , and a(k) represent the operator valued Fourier co-
efficients. Rearranging the momentum integration, we obtain the Lorentz covariant
expansion
7
d4 k + ,
φ̂(x) = 2πδ(k 2 − m2 )θ(k 0 ) a(k)e−ik·x + a† (k)eik·x .
(2π) 4

Integrating over k 0 , and making use of the identity

7 7
d4 k d4 k
2πδ(k − m )θ(k ) =
2 2 0
δ(k02 − ωk2 )θ(k 0 )
(2π) 4 (2π)3
7 7
d4 k d4 k 1
= δ [(k0 − ω k )(k0 + ω k )] θ(k 0
) = [δ(k0 − ωk ) + δ(k0 + ωk )] θ(k 0 )
(2π) 3 (2π)3 2k0
7 7 7
d3 k dk0 d3 k
= δ(k 0 − ω k )θ(k 0
) = ,
(2π) 3 2k0 (2π)3 2ωk

one obtains
7
d3 k ) *
φ̂(x) = a(k)e−ik·x + a† (k)eik·x .
(2π)3 2ωk

More compactly, making use of the orthonormality of the basis

7
1 ↔
fk = 3 e−ik·x , fk∗ (x)i ∂ 0 fk! (x)d3 x = δ 3 (k − k! ),
(2π) 2ωk
3

↔
where A ∂0 B ≡ A∂t B − (∂t A)B, we obtain
7
d3 k + ,
φ̂(x) = 3 a(k)fk (x) + a† (k)fk∗ (x) .
(2π)3 2ωk
10
Note that the field operators obey the equation of motion,
∂H
π̇(x, t) = − = ∇2 φ − m2 φ .
∂φ(x, t)

Together with the relation π = φ̇, one finds (∂ 2 + m2 )φ = 0.

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15.4. QUANTIZATION OF RELATIVISTIC FIELDS 182

Similarly,
7
d3 k + ,
π̂(x) ≡ ∂0 φ̂(x) = 3 iωk −a(k)fk (x) + a† (k)fk∗ (x) .
(2π)3 2ω k

Making use of the orthogonality relations, the latter can be inverted to give
3 7 ↔ 3 7 ↔
a(k) = (2π)3 2ωk d3 xfk∗ (x)i ∂0 φ̂(x), a† (k) = (2π)3 2ωk d3 xφ̂(x)i ∂0 fk (x) ,

or, equivalently,
7 / 0 7 / 0
a(k) = d3 x ωk φ̂(x) − iπ̂(x) e−ik·x , a (k) =
†
d3 x ωk φ̂(x) + iπ̂(x) eik·x .

With these definitions, it is left as an exercise to show

+ , + ,
a(k), a† (k! ) = (2π)3 2ωk δ 3 (k − k! ), [a(k), a(k! )] = a† (k), a† (k! ) = 0 .

The field operators a† and a can therefore be identified as operators that create and
annihilate bosonic particles. Although it would be tempting to adopt a different
normalisation wherein [a, a† ] = 1 (as is done in many texts), we chose to adopt the
convention above where the covariance of the normalisation is manifest. Using this
representation, the Hamiltonian is brought to the diagonal form
7
d3 k ωk + † ,
Ĥ = a (k)a(k) + a(k)a† (k) ,
(2π) 2ωk 2
3

a result which can be confirmed by direct substitution.

Defining the vacuum state |Ω4 as the state which is annhiliated by a(k), a single
particle state is obtained by operating the creation operator on the vacuum,

|k4 = a† (k)|Ω4 .

Then 3k! |k4 = 3Ω|a(k! )a† (k)|Ω4 = 3Ω|[a(k! ), a† (k)]|Ω4 = (2π)3 2ωk δ 3 (k! − k). Many-
particle states are defined by |k1 · · · kn 4 = a† (k1 ) · · · a† (kn )|Ω4 where the bosonic
statistics of the particles is assured by the commutation relations.
Associated with these field operators, one can define the total particle number
operator
7
d3 k
N̂ = 3 a† (k)a(k) .
(2π)3 2ωk

Similarly, the total energy-momentum operator for the system is given by

7
d3 k
P̂ =
µ
3 k µ a† (k)a(k) .
(2π)3 2ωk

The time component P̂ 0 of this result can be compared with the Hamiltonian above.
In fact, commuting the field operators, the latter is seen to differ from P̂ 0 by an infinite
8
constant, d3 kωk /2. Yet, had we simply normal ordered11 the operators from the
outset, this problem would not have arisen. We therefore discard this infinite constant.

15.4.2 Info: Charged Scalar Field

A generalization of the analysis above to the complex scalar field leads to the La-
grangian,

1 1
L= ∂µ φ∂ µ φ̄ − m2 |φ|2 .
2 2
11
Recall that normal ordering entails the construction of an operator with all the annihi-
lation operators moved to the right and creation operators moved to the left.

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15.4. QUANTIZATION OF RELATIVISTIC FIELDS 183

The latter can √be interpreted as the superposition of two independent scalar fields
φ = (φ1 +iφ2 )/ 2, where, for each (real) component φ†r (x) = φr (x). (In fact, we could
as easily consider a field with n components.) In this case, the canonical quantisation
of the classical fields is achieved by defining (exercise)
7
d3 k + ,
φ̂(x) = 3 a(k)fk (x) + b† (k)fk∗ (x) .
(2π) 2ωk
3

(similarly φ† (x)) where both a and b obey bosonic commutation relations,

+ , + ,
a(k), a† (k! ) = b(k), b† (k! ) = (2π)3 2ωk δ 3 (k − k! ),
+ ,
[a(k), a(k! )] = [b(k), b(k! )] = a(k), b† (k! ) = [a(k), b(k! )] = 0 .

With this definition, the total number operator is given by

7
d3 k + † ,
N̂ = 3 a (k)a(k) + b† (k)b(k) ≡ N̂a + N̂b ,
(2π) 2ωk
3

while the energy-momentum operator is defined by

7
d3 k + ,
P̂ µ = 3 k µ a† (k)a(k) + b† (k)b(k) .
(2π) 2ωk
3

Thus the complex scalar field has the interpretation of creating different sorts of
particles, corresponding to operators a† and b† . To understand the physical interpre-
tation of this difference, let us consider the corresponding charge density operator,
↔ 8
ĵ0 = φ̂† (x)i ∂ 0 φ(x). Once normal ordered, the total charge Q = d3 xj0 (x) is given
by
7
d3 k + † ,
Q̂ = 3 a (k)a(k) − b† (k)b(k) = N̂a − N̂b .
(2π) 2ωk
3

From this result we can interpret the particles as carrying an electric charge, equal
in magnitude, and opposite in sign. The complex scalar field is a theory of charged
particles. The negative density that plagued the Klein-Gordon field is simply a man-
ifestation of particles with negative charge.

15.4.3 Info: Dirac Field

The quantisation of the Klein-Gordon field leads to a theory of relativistic spin zero
particles which obey boson statistics. From the quantisation of the Dirac field, we
expect a theory of Fermionic spin 1/2 particles. Following on from our consideration
of the Klein-Gordon theory, we introduce the Lagrangian density associated with the
Dirac equation (exercise)

L = ψ̄ (iγ µ ∂µ − m) ψ ,

↔
(or, equivalently, L = ψ̄( 12 iγ µ ∂ µ −m)ψ). With this definition, the corresponding
canonical momentum is given by ∂ψ̇ L = iψ̄γ 0 = iψ † . From the Lagrangian density,
we thus obtain the Hamiltonian density,

H = ψ̄ (−iγ · ∇ + m) ψ ,

which, making use of the Dirac equation, is equivalent to H = ψ̄iγ 0 ∂0 ψ = ψ † i∂t ψ.

For the Dirac theory, we postulate the equal time anticommutation relations
9 :
ψα (x, t), iψβ† (x! , t) = iδ 3 (x − x! )δαβ ,

(or, equivalently {ψα (x, t), iψ̄β (x! , t)} = γαβ

0
δ 3 (x − x! )), together with

; <
{ψα (x, t), ψβ (x! , t)} = ψ̄α (x, t), ψ̄β (x! , t) = 0 .

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15.5. THE LOW ENERGY LIMIT OF THE DIRAC EQUATION 184

Using the general solution of the Dirac equation for a free particle as a basis set,
together with the intuition drawn from the study of the complex scalar field, we may
with no more ado, introduce the field operators which diagonalise the Hamiltonian
density
2 7
= d3 k - .
ψ(x) = ar (k)u(r) (k)e−ik·x + b†r (k)v (r) (k)eik·x
r=1
(2π) 2ωk
3

7
d3 k - † .
=2
ψ̄(x) = a (k)ū (r)
(k)eik·x
+ b r (k)v̄ (r)
(k)e−ik·x
,
r=1
(2π)3 2ωk r

where the annihilation and creation operators also obey the anticommutation rela-
tions,
; < ; <
ar (k), a†s (k! ) = br (k), b†s (k! ) = (2π)3 2ωk δrs δ 3 (k − k! )
; < ; <
{ar (k), as (k! )} = a†r (k), a†s (k! ) = {br (k), bs (k! )} = b†r (k), b†s (k! ) = 0 .
The latter condition implies the Pauli exclusion principle a† (k)2 = 0. With this
definition, a(k)u(k)e−ik·x annilihates a postive energy electron, and b† (k)v(k)eik·x
creates a positive energy positron.
From these results, making use of the expression for the Hamiltonian density
operator, one obtains
=2 7
d3 k + ,
Ĥ = ωk a†r (k)ar (k) − br (k)b†r (k) .
r=1
(2π) 2ωk
3

Were the commutation relations chosen as bosonic, one would conclude the existence
of negative energy solutions. However, making use of the anticommutation relations,
and dropping the infinite constant (or, rather, normal ordering) one obtains a positive
definite result. Expressed as one element of the total energy-momentum operator, one
finds
2 7
= d3 k + ,
P̂ µ = k µ a†r (k)ar (k) + b†r (k)br (k) .
r=1
(2π) 2ωk
3

Finally, the total charge is given by

7 7
Q̂ = ĵ 0 d3 x = d3 xψ † ψ = N̂a − N̂b .
8
where N̂ represents the total number operator. Na = d3 k a† (k)a(k) is the number
8
of the particles and Nb = d3 k b† (k)b(k) is the number of antiparticles with opposite
charge.

15.5 The low energy limit of the Dirac equation

To conclude our abridged exploration of the foundations of relativistic quan-
tum mechanics, we turn to the interaction of a relativistic spin 1/2 particle
with an electromagnetic field. Suppose that ψ represents a particle of charge
q (q = −e for the electron). From non-relativistic quantum mechanics, we ex-
pect to obtain the equation describing its interaction with an EM field given
by the potential Aµ by the minimal substitution

pµ )−→ pµ − qAµ ,

where A0 ≡ ϕ. Applied to the Dirac equation, we obtain for the interaction of

a particle with a given (non-quantized) EM field, [γµ (pµ − qAµ ) − m]ψ = 0,
or compactly

(+ p − q+A − m)ψ = 0 .

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15.5. THE LOW ENERGY LIMIT OF THE DIRAC EQUATION 185

Previously, in chapter 9, we explored the relativistic (fine-structure) cor-

rections to the hydrogen atom. At the time, we alluded to these as the leading
relativistic contributions to the Dirac theory. In the following section, we will
explore how these corrections are derived.
In the Dirac-Pauli representation,
! " ! "
0 σ I2 0
α= , β= .
σ 0 0 −I2

we have seen that the plane-wave solution to the Dirac equation for particles
can be written in the form
! "
χ
ψp (x) = N cσ ·p̂ ei(px−Et)/! ,
mc2 +E
χ

where we have restored the parameters ! and c. From this expression, we can
see that, at low energies, where |E − mc2 | - mc2 , the second component of
the bispinor is smaller than the first by a factor of order v/c. To obtain the
non-relavistic limit, we can exploit this asymmetry to develop a perturbative
expansion of the coefficients in v/c.
Consider then the Dirac equation for a particle moving in a potential
(φ, A). Expressed in matrix form, the Dirac equation H = cα · (−i!∇ −
c A) + mc β + eφ is expressed as
e 2

! "
mc2 + eφ cσ · (−i!∇ − ec A)
H= .
cσ · (p̂ − qc A) −mc2 + qφ

Defining the bispinor ψ T (x) = (ψa (x), ψb (x)), the Dirac equation translates to
the coupled equations,
q
(mc2 + eφ)ψa + cσ · (p̂ − A)ψb = Eψa
c
q
cσ · (p̂ − A)ψa − (mc2 − qφ)ψb = Eψb .
c
Then, if we define W = E − mc2 , a rearrangement of the second equation
obtains
1 q
ψb = cσ · (p̂ − A)ψa .
2mc2 + W − qφ c
q
Then, at zeroth order in v/c, we have ψb $ 2mc 1
2 cσ ·(p̂− c A)ψa . Substi-
tuted into the first equation, we thus obtain the Pauli equation Hnon−rel ψa =
W ψa , where
1 - q .2
Hnonr el = σ · (p̂ − A) + qφ .
2m c
Making use of the Pauli matrix identity σi σj = δij + i$ijk σk , we thus obtain
the familiar non-relativistic Schrödinger Hamiltonian,

1 q q!
Hnon rel = (p̂ − A)2 − σ · (∇ × A) + qφ .
2m c 2mc

As a result, we can identify the spin magnetic moment

q! q!
µS = σ= Ŝ ,
2mc mc

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15.5. THE LOW ENERGY LIMIT OF THE DIRAC EQUATION 186

with the gyromagnetic ratio, g = 2. This compares to the measured value

of g = 2 × (1.0011596567 ± 0.0000000035), the descrepency form 2 being at-
tributed to small radiative corrections.
Let us now consider the expansion to first order in v/c. Here, for sim-
plicity, let us suppose that A = 0. In this case, taking into account the next
order term, we obtain
! "
1 V −W
ψb $ 1 + cσ · p̂ψa
2mc2 2mc2
where V = qφ. Then substituted into the second equation, we obtain
1 2
1 1
(σ · p̂) +
2
(σ · p̂)(V − W )(σ · p̂) + V ψa = W ψa .
2m 4m2 c2
At this stage, we must be cautious in interpreting ψa as a complete non-
relavistic wavefunction with leading relativistic corrections. To find the true
wavefunction, we have to consider the normalization. If we suppose that the
original wavefunction is normalized, we can conclude that,
7 7 / 0
d3 xψ † (x, t)ψ(x, t) = d3 x ψa† (x, t)ψa (x, t) + ψb† (x, t)ψb (x, t)
7 7
† 1
$ d xψa (x, t)ψa (x, t) +
3
d3 xψa† (x, t)p̂2 ψa (x, t) .
(2mc)2
Therefore, at this order, the normalized wavefunction is set by, ψs = (1 +
1
8m2 c2
p̂2 )ψa or, inverted,
! "
1
ψa = 1 − p̂2
ψs .
8m2 c2
Substituting, then rearranging the equation for ψs , and retaining terms of
order (v/c)2 , one ontains (exercise) Ĥnon−rel ψs = W ψs , where

p̂2 p̂4 1 1
Ĥnon−rel = − + (σ · p̂)V (σ · p̂) + V − (V p̂2 + p̂2 V ) .
2m 8m3 c2 4m2 c2 8m2 c2
Then, making use of the identities,

[V, p̂2 ] = !2 (∇2 V ) + 2i!(∇V ) · p̂

(σ · p̂)V = V (σ · p̂) + σ · [p̂, V ]
(σ · p̂)V (σ · p̂) = V p̂2 − i!(∇V ) · p̂ + !σ · (∇V ) × p̂ ,

we obtain the final expression (exercise),

p̂2 p̂4 ! !2
Ĥnon−rel = − + σ · (∇V ) × p̂ + (∇2 V ) .
2m 8m3 c2 >4m2 c2 ?@ A > 8m2 c2
?@ A
spin−orbit coupling Darwin term

The second term on the right hand side represents the relativistic correction
to the kinetic energy, the third term denotes the spin-orbit interaction and
the final term is the Darwin term. For atoms, with a central potential, the
spin-orbit term can be recast as
!2 1 !2 1
ĤS.O. = σ · (∂r V )r × p̂ = (∂r V )σ · L̂ .
4m c
2 2 r 4m2 c2 r
To address the effects of these relativistic contributions, we refer back to chap-
ter 9.

Advanced Quantum Physics

Chapter 16

Problem sets

Before starting these problems, you might want to revise some of the examples
from the Part IB Quantum Physics course. The examples marked with a † are
typically more challenging and are the ones to omit if your time is very short, or if
you are finding the course difficult. Some of the questions involve a routine piece
of bookwork. This is the kind of thing you will have to do in the exam. You are
strongly encouraged to do these parts and get feedback in supervisions.

16.1 Problem Set I

1. Quantum mechanics in one-dimension: The following question introduces
the concept of a scattering matrix (or S-matrix) in relation to scattering
from a potential in one dimension. These concepts will prepare the ground
for the study of the three-dimensional scattering problem addressed later in
the course.
Consider a localized potential in one-dimension (i.e. a potential that is
non-zero only over a finite region in space) subject to a beam of quantum
particles incident from the left and from the right (see figure). Outside
the region of the potential, we know that the wavefunction Be−ikx Ceikx
√ of the par-
ticles is described by a plane wave of wavevector k = 2mE/�. The
relation between the incoming and outgoing components of the plane ����
wave are specified by a scattering matrix (commonly referred to as Aeikx De−ikx
the (S-matrix)), i.e. referring to the figure,
� � � �� �
C S11 S12 A
|Ψout � = S|Ψin � ⇒ =
B S21 S22 D

�a) Consider the action of the probability current operator on a plane

wave and hence show that conservation of probability implies that
|A|2 + |D|2 = |B|2 + |C|2 . Show that this condition is equivalent to
demanding that the S-matrix is unitary, i.e. S † S = �. For matrices
which are unitary, the eigenvalues have unit magnitude,1 eiθ – i.e.
two scattering phase shifts, in general functions of k, completely
describe the scattering in one dimension.

For the case of a symmetric potential, V (x) = V (−x), the S-matrix

assumes the simple form
� �
t r
S= �
r t
1
The proof is as follows: for an eigenvector |v�, such that S|v� = λ|v�, we have the norm
�v|S † S|v� = |λ|2 �v|v� = �v|v�, i.e. |λ|2 = 1.

Advanced Quantum Physics

16.1. PROBLEM SET I 188

where r and t are the reflection and transmission amplitudes. re−ikx teikx

eikx
�b) Show that unitarity demands that rt∗ + r∗ t = 0 and |r|2 + |t|2 = 1,
and hence that |r ± t|2 = 1. Find θ1 and θ2 in terms of r and t.
What is the difference in phase between r and t?
�c) By matching the boundary conditions, show the elements of the S-
2 k2
matrix for the scattering of particles of mass m and energy E = �2m V0
γ
from a δ-function potential, aV0 δ(x), are given by r = − γ+ik and
ik maV0
t = γ+ik , where γ = �2 . Obtain the corresponding scattering
phase shifts.

2. Operator methods: This problem addresses simple relations that follow from
the orthogonality of eigenfunctions and the time-development of wavefunc-
tions.
The Hamiltonian Ĥ has two normalized eigenstates |ψ1 � and |ψ2 � which
correspond to different eigenvalues E1 and E2 .

(a) Show that |ψ1 � and |ψ2 � are orthogonal.

(b) For an observable  where Â|ψ1 � = |ψ2 � and Â|ψ2 � = |ψ1 �, calculate
the eigenvalues and eigenvectors (which are combinations of |ψ1 �
and |ψ2 �).
(c) Assuming that at t = 0 the system is in the state |ψ(t = 0)� =
√1 [|ψ1 � − |ψ2 �], find the state of the system |ψ(t)� at time t and
2
show that the probability of the system returning to its initial state
is given by P = cos2 [(E1 − E2 )t/2�].

3. Operator methods: This question relates to the probem of coherent or

Glauber states. It is included in the problem set as it presents a useful
arena in which to practice operator methods. The aim of the problem is
to explore properties of coherent states and establish their connection to
classical dynamics of the harmonic oscillator.

�a) By using the commutation relation [a� a† ] = 1, show that Hint: To prove this result most
† †
straightforwardly, consider the β
e−βa aeβa = β + a . derivative of this expression.
†
Using this result, show that |β� = N eβa |0� is a coherent state, i.e.
2
a|β� = β|β�. Finally, show that the normalization, N = e−|β| /2 .
�b) Calculate the expectation values, x0 = �x̂� and p0 = �p̂�, with Hint: Remember how creation
respect to |β� and, by considering �x̂2 � and �p̂2 �, show that and annihilation operators are
related to the phase space opera-
�2 tors x̂ and p̂. Also, note that the
(Δp)2 (Δx)2 = �
4 Hermitian conjuate of the eigen-
value equation a|β� = β|β� leads
where Δp = p̂ − �p̂� (similarly x).
to the relation �β|a† = �β|β ∗ .
�c) To determine the coordinate representation to the coherent state,
ψ(x) = �x|β�, it is helpful to revert back to the expression for
a as a differential operator. Show that the eigenvalue equation
a|β� = β|β� translates to the equation,
� �
�
x+ ∂x ψ(x) = βψ(x) .
mω

Advanced Quantum Physics

16.1. PROBLEM SET I 189

Show that this equation has the solution

(x − x0 )2
� �
p0 x
ψ(x) = N exp − +i �
4(Δx)2 �
where x0 and p0 are defined in part (b) above.
�d) By expressing |β� in the number basis, show that
ωt
|β(t)� = e−i 2 |βe−iωt � .

As a result, deduce expressions for x0 (t) and p0 (t) and show they
represent solutions to the classical equations of motion. How does
the width of the coherent state wavepacket evolve with time?

4. Charged particles in a magnetic field: In lectures, we studied the mo-

tion of an electron in a uniform magnetic field working in the Landau
gauge, A = (−By� 0� 0). With this gauge choice, the Hamiltonian may
be straightforwardly brought to a quantum harmonic oscillator form. In this
question, we will address the problem by working the “symmetric” gauge
A = (−By/2� Bx/2� 0). The advantage of this gauge choice is that it fa-
cilitates the development of the many-particle wavefunction in an aesthetic
and useful form.

�a) A spinless electron of charge q = −e is confined to the xy-plane

and subject to a perpendicular magnetic field B = Bêz . Working
in the symmetric gauge A = (−y� x� 0)B/2, show that the electron
Hamiltonian is given by
� �2 � �2
1 1 1 1
Ĥ = p̂x − mωy + p̂y + mωx �
2m 2 2m 2
eB
where ω = m denotes the cyclotron frequency. Physicists often choose to work
�b) If units are chosen such that ω = m = � = 1, show that the Hamil- in dimensionless units setting
� = 1, etc. Think about what
tonian can be recast in the dimensionless form this choice entails and, at each
1� y �2 1 � x �2 stage of the problem, try to in-
Ĥ = −i∂x − + −i∂y + . fer how dimensionful parameters
2 2 2 2
can be restored.
�c) Introducting the complex coordinate, z̄ = x + iy and the complex
conjugate, z = x − iy, the corresponding derivatives are given by
∂
∂z̄ = 12 (∂x − i∂y ), and ∂z = 12 (∂x + i∂y ) where ∂z ≡ ∂z . From this
definition, confirm that The choice z = x − iy (as op-
posed to z = x + iy) is made
[z� ∂z ] = [z̄� ∂z̄ ] = −1� [z� ∂z̄ ] = [z̄� ∂z ] = 0 . on purely aesthetic grounds – see
the wavefunction below. Also,
Show that the operators, following convention in this sub-
√ � z� √ � z̄ � ject, we have chosen to write the
a = 2 ∂z̄ + � a† = 2 −∂z + � complex conjugate as z̄ and not
4� 4�
√ � z̄ √ � z z ∗ .)
b = 2 ∂z + � b† = 2 −∂z̄ + �
4 4
fulfil the commutation relations [a� a† ] = [b� b† ] = 1 characteristic of
creation and annihilation operators. Applied to the Hamiltonian,
show that
1
Ĥ = a† a + �
2

Advanced Quantum Physics

16.1. PROBLEM SET I 190

independent of b, i.e. a quantum harmonic oscillator. As a result,

we can identify a Landau level Hamiltonian with the level set by
the eigenvalue, n of the number operator, n̂ = a† a.
�d) Show that the angular momentum operator takes the form,

L̂z = −(b† b − a† a)� .

Therefore, if we define the eigenvalues of L̂z as −m� (with the

sign following an accepted convention), the quantum numbers m
can take values m = −n� −n + 1� · · · � 0� 1� · · ·. The corresponding
(normalized) states of Landau level, n, and angular momentum, m,
are given by

(b† )m+n (a† )n

|n� m� = � √ |0� 0� �
(m + n)� n�

where |0� 0� denotes the zero angular momentum ground state of

the lowest Landau level.
�e) Going back to the definition of the annihilation operator, show that
the ground state in the real space representation is given by,2 Note that, for the ground state,
we must have a|0� 0� = b|0� 0� =
1 0.
�r|0� 0� = √ e−z̄z/4 .
2π
Finally, show that in the lowest Landau level,
1
�r|0� m� = √ z m e−z̄z/4 �
m
2π2 m�
i.e. aside from the Gaussian factor, the states of the lowest Landau
level are given by a polynomial in z – they are said to be analytic
functions of z.
�f ) The last part of this problem anticipates our studies of the many-particle
fermionic system in chapter 8 and should not be attempted until this
ground is covered. In this chapter, we will show that the properly an-
tisymmetrized many-particle wavefunction of a non-interacting system
of N identical spinless electrons (fermions) is given by the Slater de-
terminant, ψ(r1 � r2 � · · ·) = detij φi (rj ) where φi (r) denote eigenstates
of the single-particle problem.
Using the identity
� �
� 1 1 1 ··· �
� �
� z1 z2 z3 · · · � �
� z2 z2 z2 · · · � = (zj − zk ) �
� �
� 1 2 3 �
� . .. .. . . �� j<k
� .. . . .

known as a Vandemonde determinant, show that the ground

state wavefunction of the filled lowest Landau level is given by
� �
� 1� 2
ψ(r1 � r2 � · · ·) = (zj − zk ) exp − |zi | .
4
j<k i

2
In the symmetric gauge, we therefore find that the Landau level states are localized in
both x and y directions. This contrasts with what was found from the Landau gauge condi-
tion where states were localized along only one direction. Of course, there is no contradiction
between these two representations: since the Landau levels have a huge degeneracy, we are
at liberty to reconstruct states within the basis.

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16.1. PROBLEM SET I 191

Note that, as required, the wavefunction is antisymmetric under the

exchange of any two fermions. This expression also emphasizes the
exclusion character of the fermionic system with the wavefunction
vanishing as any two particles move together.

5. Spin: This question develops the concept of a spinor wavefunction. Hint: You can find the relevant
spin operator by taking the dot
Using the Pauli matrices, σx , σy and σz , write down the operator corre-
product of the vector σ with a
sponding to a component of spin along the axis (θ� φ) in spherical polar unit vector in the desired direc-
coordinates. Show that the eigenvalues of spin in this direction are ±�/2 tion.
(as expected), and deduce the corresponding wavefunctions. Hence, in-
fer the wavefunctions for particles whose spins are aligned along the +x,
−x, +y and −y directions.

6. Spin: This problem addresses the addition of spin angular momenta.

Consider two identical spin 1/2 fermions, and let χ+ (i) represent the
state of particle i with spin up, and χ− (i) the state with spin down.
Write down the four possible states of the system which have definite
exchange symmetry.
Show that Ŝ2 = Ŝ+ Ŝ− + Ŝz2 − �Ŝz , where the spin raising and lowering
operators are given by Ŝ± = Ŝx ± iŜy . Using this result, or otherwise,
show that the four states of definite exchange symmetry are eigenstates
of Ŝ2 and find the corresponding eigenvalues and hence the total spin
quantum number for each state.
At a given moment, the system is in a state,
� �
2 1
ψ= χ+ (1)χ− (2) + χ− (1)χ+ (2) .
3 3
What is the probability of a measurement of the total spin giving the
result S = 1?
Hint: Write the wavefunction
corresponding to spin +� in the
7. † Spin: This is a challenging problem which addresses several important x direction using as a basis the
aspects of the coursework: quantum spin algebra, time-evolution, and spin eigenstates of Ŝz . Then write the
precession in a field. time dependence of this wave-
function in the presence of the
A Stern-Gerlach apparatus is used as a filter which rejects para-H2 and uniform field B, and find the
passes molecules of ortho-H2 (which has resultant nuclear spin one) with fraction of the Sx = +� state in
spin component +� in the x direction travelling in the y direction. A this wavefunction at a later time.
magnetic field B in the z direction acts over 20mm of path between two You can also obtain the same re-
such filters in series, and it is found that no molecules of kinetic energy sult from a classical precession
0.025eV emerge when B = 1.8(n + 1/2) × 10−3 T, where n is an integer. argument.
You may note that J± |j� m� =
Explain this phenomenon and deduce a value for the magnetic moment
�[j(j +1)−m(m+1)]1/2 |j� m±1�.
of the proton. (Part II 1966)

8. Spin: We have seen that the “ladder operator” formalism provides a frame-
work in which to define and classify the states of the quantum harmonic
oscillator. In the following, we will see that the same ladder operator for-
malism provides a representation of the quantum spin algebra. This repre-
sentation, known as the Holstein-Primakoff transformation, can be used to

Advanced Quantum Physics

16.1. PROBLEM SET I 192

develop a controlled perturbation theory of spin Hamiltonians. For present

purposes, it also gives us an opportunity to practice the operator formalism
and spin algebra.
According to the quantum spin algebra, the spin operators are defined
by the commutation relations, [Ŝ i � Ŝ j ] = i��ijk Ŝ k , where �ijk denotes the
antisymmetric tensor. According to the Holstein-Primakoff transforma-
tion,3 it is stated that the quantum mechanical spin S operators can be
represented by
�1/2
√ a† a
�
− †
Ŝ = � 2S a 1 − � Ŝ + = (Ŝ − )† � Ŝ z = �(S − a† a) �
2S

where the ladder operators a and a† obey the usual commutation rela- Hint: If you find yourself
tions, [a� a† ] ≡ aa† − a† a = 1.4 Making use of these relations, show that expanding the square root,
this definition is indeed consistent with the quantum spin algebra, i.e. you should stop and consider
[Ŝ + � Ŝ − ] = 2�Ŝ z . whether there is a simpler
method...
Comments: Physically, the ladder operators simply “count” the number
of “spin deviations” away from êz . For large spin, S – the analogue the
semi-classical limit for quantum mechanical spins
√ –†the Holstein-Primakoff
transformation
√ affords the expansion, S = � 2S a +O(S −1/2 ) and S + =
−

� 2S a + O(S −1/2 ). In this limit, quantum spin models typically become

bilinear (i.e. quadratic) in ladder operators and can be “diagonalized” (i.e.
solved) in the same manner as the quantum harmonic oscillator Hamiltonian.

9. Addition of angular momenta: The addition of two or more angular mo-

menta is a common problem which will arise this year in atomic, molecular,
nuclear and particle physics. It is therefore very important to understand
the basic principles.
Consider the addition of two angular momenta, �1 = 1 and �2 = 2. Ac-
cording to quantum mechanics, the possible values for the total angular
momentum quantum number L range from �1 + �2 to |�1 − �2 |, i.e. 3, 2, 1
in this case. Tabulate the possible values of the corresponding quantum
numbers m1 , m2 and M = m1 + m2 (i.e. those relating to L̂z ), and show
that the values of M correspond to the expected values of L. Repeat for
the case �1 = 3, �2 = 1.
For the case �1 = 2 and �2 = 1, the state |L = 3� M = 3� can be written
down straightforwardly as |�1 = 2� m1 = 2� ⊗ |�2 = 1� m2 = 1�. Use
ladder operators to construct explicitly the state |L = 3� M = 2� and
then orthogonality to construct the state |L = 2� M = 2� in terms of
the |�1 � m1 � ⊗ |�2 � m2 � states. This method can obviously be extended to
construct all such states.

10. Addition of angular momenta:

Write down the commutation relations between the angular momentum
operators Jx , Jy , and Jz (hats not shown�).
3
T. Holstein and H. Primakoff, Field dependence of the intrinsic domain magnetization
of a ferromagnet, Phys. Rev. 58, 1098 (1940).
4
If you feel disturbed by the concept of the “square root of an operator”, you should
†
think of it as defined by a Taylor expansion in the argument, a2sa .

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16.1. PROBLEM SET I 193

�a) Show that the operators J± = Jx ± iJy act as raising and lower-
ing operators for the z-component of angular momentum, by first
calculating the commutator [Jz � J± ].
�b) State the allowed values of the total spin angular momentum for a
system of three electrons.
�c) The ‘coupled basis’ state |S = 3/2� mS = 3/2� (an eigenstate of
total spin) is also a state of the ‘uncoupled basis’, which may be You may note that J± |j� m� =
denoted by | ↑↑↑� ≡ | ↑� ⊗ | ↑� ⊗ | ↑�. By an application of total �[j(j +1)−m(m+1)]1/2 |j� m±1�.
spin lowering operator, show that
1
|S = 3/2� mS = 1/2� = √ (| ↓↑↑� + | ↑↓↑� + | ↑↑↓�) .
3

Advanced Quantum Physics

16.1. PROBLEM SET I 197

Answers: Problem set I

1. (a) In one dimension, the current operator is specified by ĵ = 2m 1
(ψ ∗ p̂ψ +
ψ(p̂ψ) ). Applied to the left hand side of the system (outside the region
∗

of the potential), where ψ(x) = Aeikx + Be−ikx , we have jleft = !k m (|A| −

2
!k
|B| ); similarly jright = m (|C| − |D| ). Current conservation demands
2 2 2

that jleft = jright , i.e. |A|2 + |D|2 = |C|2 + |B|2 – all of the incoming beam
is transferred to the outgoing beam, a statement of particle conservation.
This conservation of current can be written as "Ψin |Ψin # = "Ψout |Ψout #.
Therefore, using the expression for |ψout #, we have

"Ψin |Ψin # = "Ψout |Ψout # = "Ψin !"#$

S † S Ψin # ,
!
=I

leading to the unitarity condition.

(b) From the unitarity condition, it follows that
% 2 &
|t| + |r|2 rt∗ + r∗ t
S†S = I =
rt∗ + r∗ t |t|2 + |r|2

Comparing the matrix elements, we obtained the required result.

(c) For the δ-function scattering problem, the wavefunction is given by
' ikx
e + re−ikx x < 0
ψ(x) =
teikx x>0

For the δ-function potential, the wavefunction must remain continuous as

x = 0, and
2maV0
∂x ψ|+! − ∂x ψ|−! = − ψ(0) .
!2
This translates to the conditions 1 + r = t, and ik(t − 1 + r) = − 2maV0
!2 t.
As a result, we obtain
ik
t= ,
ik + maV
!2
0

as required. Using the result from (b), since the potential is symmetric,
we have
% &
t ik + γ k2 −ik + γ γ 2 γ2
r = ∗ (|t| − 1) = −
2 2
− 1 = =
t −ik + γ k 2 + γ 2 ik + γ k 2 + γ 2 (ik + γ)2

As a result, we obtain the required expression for r.

2. (a) We are told that Ĥ|ψ1 # (= E1 |ψ1 # and Ĥ|ψ

( 2 # = E2 |ψ2 #, where E1 $= E2 .
Therefore "ψ1 |Ĥ|ψ2 # = ψ1∗ Ĥψ2 dx = ψ1∗ E2 ψ2 dx = E2 "ψ1 |ψ2 #. Since
Ĥ is Hermitian, we can write
) )
"ψ1 |Ĥ|ψ2 # = (Ĥψ1 )∗ ψ2 dx = (E1 ψ1 )∗ ψ2 dx = E1∗ "ψ1 |ψ2 # = E1 "ψ1 |ψ2 # ,

since E1 and E2 are real. Therefore, (E1 −E2 )"ψ1 |ψ2 # = 0 and, if E1 $= E2
then "ψ1 |ψ2 # = 0, i.e. |ψ1 # and |ψ2 # are orthogonal.
(b) If Â|ψ1 # = |ψ2 # and Â|ψ2 # = |ψ1 #, then adding them, Â(|ψ1 # + |ψ2 #) =
|ψ1 # + |ψ2 # and subtracting, Â(|ψ1 # − |ψ2 #) = |ψ2 # − |ψ1 # = −(|ψ1 # − |ψ2 #).
Hence we have an eigenvector of a = +1 corresponding to a normalized
eigenvector √12 (|ψ1 # + |ψ2 #) and an eigenvalue a = −1 corresponding to
eigenvector √12 (|ψ1 # − |ψ2 #).

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16.1. PROBLEM SET I 198

(c) The time-dependent Schrödinger equation is Ĥψ = Eψ = i!∂t ψ, hence

ψ(t) = ψ(t = 0)e−iEt/! . Since |ψ1 # and |ψ2 # are eigenstates of the Hamil-
tonian Ĥ then we can write, |ψ(t)# = √12 [|ψ1 #e−iE1 t/! − |ψ2 #e−iE2 t/! ].
1 ** *2
*
P = |"ψ(t = 0)|ψ(t)#|2 = *["ψ1 | −" ψ2 |][|ψ1 #e−iE1 t/! − |ψ2 #e−iE2 t/! ]*
4
1
= [1 + cos((E1 − E2 )t/!)] = cos2 ((E1 − E2 )t/2!)
2

3. (a) Differentiating the left hand side of the given expression with respect to β,
one obtains
† †
e−βa [a, a† ] eβa = 1 .
! "# $
=1
† †
Integrating, we therefore have that e−βa aeβa = β+“integration constant$$ .
By setting β = 0 we can deduce that the “constant” must be a yielding
the required result. Using this result, we have that
† † †
e−βa a|β# = e!−βa"#aeβa$ |0# = (β + a)|0# = β|0# .
=β+a

Lastly, to obtain the normalization, we have that

+∞
∗ (β ∗ a)n
"β|β# = N 2 "0|eβ a |β# = N 2 "0| |β#
n=0
n!
+∞
(β ∗ β)n 2 !
= N2 "0|β# = N 2 e|β| = 1 .
n=0
n!
2
i.e. N = e−|β| /2 as required.
(b) For the harmonic oscillator, the creation and annihilation
, operators are
!
related to the phase space operators by x̂ = 2mω (a + a ), and p̂ =
†
,
−i !mω 2 (a − a ). Therefore, we have
†

- -
! !mω
"x̂# = (β + β ),
∗
"p̂# = −i (β − β ∗ ) .
2mω 2
Then, using the identity (∆x)2 = "(x − "x#)2 # = "x2 # − "x#2 , we have
! !
"x2 # = "β|(a2 + aa† + a† a + (a† )2 |β# = (1 + (β + β ∗ )2 ),
2mω 2mω
!mω !
"p̂2 # = − "β|(a2 − aa† − a† a + (a† )2 |β# = − (−1 + (β − β ∗ )2 ) .
2 2mω
!
As a result, we find that ∆x = 2mω and ∆p = !mω2 leading to the required
expression.
(c) The equation follows simply from the definion of the operator a and the
solution may be checked by substitution.
(d) Using the time-evolution of the stationary states, |n(t)# = e−iEn t/! |n(0)#,
where En = !ω(n + 1/2), it follows that
2 βn
|β(t)# = e−iωt/2 e−|β| /2
√ e−inωt |n# = e−iωt/2 |e−iωt β# .
n!
Therefore, during the time-evolution, the coherent state form is preserved
but the centre of mass and momentum follow that of the classical oscilla-
tor,
x0 (t) = A cos(ϕ + ωt), p0 (t) = mωA sin(ϕ + ωt) .
The width of the wavepacket remains constant.

Advanced Quantum Physics

16.1. PROBLEM SET I 199

4. (a) Starting with the electron Hamiltonian Ĥ = 2m 1

(p̂ − qA)2 , substitution of
the expression for the vector potential leads to the required result.
(b) Setting ω = m = ! = 1, we immediately obtained the required dimension-
less form of the Hamiltonian.
(c) Straightforward substitution of the differential operators leads to the re-
quired identities. As a result, we can confirm that
2
[a, a† ] = ([∂z̄ , z̄] − [z, ∂z ]) = 1 ,
4
and similarly [b, b† ] = 1. In the complex coordinate representation,
% &2 % &2
1 i 1 1
Ĥ = −i(∂z + ∂z̄ ) − (z − z̄) + −(∂z̄ − ∂z ) + (z + z̄)
2 4 2 4
1 1 . z̄ / . z/ 1 1
= −2∂z̄ ∂z + z̄z + (z∂z̄ − z̄∂z ) = 2 −∂z + ∂z̄ + + = a† a +
8 2 4 4 2 2

(d) The angular momentum operator is given by (! = 1)

i
L̂z = (x × p̂)z = −i(x∂y − y∂x ) = − ((z + z̄)(∂z − ∂z̄ ) − (z − z̄)(∂z + ∂z̄ ))
2
. z̄ / . z/ . z/. z̄ /
= −2 −∂z + ∂z̄ + + 2 −∂z̄ + ∂z + = −(a† a − b† b) .
4 4 4 4

(e) In the coordinate representation, the condition a|0, 0# = 0 translates to the

equation
√ . z/
2 ∂z̄ + "r|0, 0# = 0
4
We thus obtain the Gaussian expression for the wavefunction. Then, using
† m
the relation |0, m# = (b√m!
)
|0, 0#, we have

1 . z̄ /m 1 −z̄z/4 1
"r|0, m# = √ 2m/2 ∂z + √ e =√ z m e−z̄z/4 ,
m! 4 2π 2π2m m!
as required.
(f ) If we populate the states of the lowest Landau with electrons, starting
from states of the lowest angular momentum m, the wavefunction is a
2
Slater determinant involving entries φm (rj ) = zjm e−|zj | /4 . Taking the
determinant, and making use of the Vandemonde determinant identity,
one obtains the required many-electron wavefunction.

5. The spin operator in the (θ, φ) direction, Ŝθφ , can be found by forming the
scalar product of the spin operator Ŝ with a unit vector in the (θ, φ) direction,
(sin θ cos φ, sin θ sin φ, cos θ). Therefore
% &
! cos θ e−iφ sin θ
Ŝθφ = .
2 eiφ sin θ − cos θ

We need the eigenvalues of the matrix, i.e.

% &% & % &
! cos θ sin θe−iφ u u
=λ .
2 sin θeiφ − cos θ v v

Eliminating u and v, we find λ2 = 1 and hence the eigenvalues of Ŝθφ are ±!/2,
as expected. Substituting the values λ = ±1 back into the equations relating
u and v, we can infer the ratios, uv = e−iφ cot(θ/2) and −e−iφ tan(θ/2). So, in
matrix notation, the eigenstates are
% & % &
cos(θ/2) sin(θ/2)
and ,
eiφ sin(θ/2) −eiφ cos(θ/2)

Advanced Quantum Physics

16.1. PROBLEM SET I 200

for eigenvalues +!/2 and −!/2 respectively. The spin states in the x-direction
are obtained by setting θ = π/2, φ = 0, and the spin states in the y-direction
are obtained by setting φ = π/4 in these general formulae.

6. The four states are given by φ1 = χ+ (1)χ+ (2), φ2 = χ− (1)χ− (2), φ3 =

√1 [χ+ (1)χ− (2) + χ− (1)χ+ (2)], and φ4 = √1 [χ+ (1)χ− (2) − χ− (1)χ+ (2)], where
2 2
φ1 , φ2 and φ3 are symmetric under particle interchange and φ4 is antisymmet-
ric.
Since Ŝ+ Ŝ− = Ŝx2 + Ŝy2 + i(Ŝy Ŝx − Ŝx Ŝy ) = Ŝ2 − Ŝz2 + !Ŝz ,

Ŝ2 = Ŝ+ Ŝ− + Ŝz2 − !Ŝz . (16.1)

(1) (2)
Noting that Ŝz = Ŝz + Ŝz , and likewise for Ŝ± , and using the basic results
for the operation of the spin operators on the single particle states,
1 (1) (1)
Ŝz(1) χ± (1) = ± !χ± (1), Ŝ∓ χ± (1) = !χ∓ (1), Ŝ± χ± (1) = 0 ,
2

we can now calculate the effect of applying Ŝ2 to each state. For example

Ŝ2 φ1 = !2 [2χ+ (1)χ+ (2) + χ+ (1)χ+ (2) − χ+ (1)χ+ (2)] = 2!2 φ1 ,

where the three terms in square brackets correspond to the three operators on
the right hand side of Eq. (16.1). Likewise φ2 . Clearly Ŝz φ3 = 0 = Ŝz φ4 , so
only the Ŝ+ Ŝ− term need be considered. We find
√
Ŝ+ Ŝ− χ+ (1)χ− (2) = Ŝ+ !χ− (1)χ− (2) = !2 (χ+ (1)χ− (2) + χ− (1)χ+ (2)) 2!2 φ3 .
√
Similarly Ŝ+ Ŝ− χ− (1)χ+ (2) = 2!2 φ3 so that

Ŝ2 φ3 = 2!2 φ3 , Ŝ2 φ4 = 0 .

Thus, φ1 , φ2 , φ3 all have eigenvalue 2!2 and hence S = 1, while φ4 has S = 0.

The state ψ is clearly an eigenstate of Ŝz with eigenvalue 0, and must therefore
be a linear combination of φ3 and φ4 . The S = 1 component is thus the φ3
term in the wavefunction with amplitude
- - - -
2 1 1 1
c3 = "φ3 |ψ# = " χ+ (1)χ− (2) + χ− (1)χ+ (2)| χ+ (1)χ− (2) + χ− (1)χ+ (2)#
3 3 2 2
0 0
= 1/3 + 1/6
√
The probability of S = 1 is therefore |c3 |2 = 3+2 2
6 = 0.971.

7. Taking as a basis the states of the Ŝz operator, we can deduce the form of the
Ŝx operator most easily from the action of the spin raising and lower operators.
Noting that, for spin S = 1, Ŝ± |S = 1, m# = ![2 − m(m + 1)]1/2 |1, m ± 1#, we
can construct the matrix elements of Ŝ± . The latter are given by
 
√ 0 1 0
†
Ŝ+ = 2!  0 0 1  , Ŝ− = Ŝ+ .
0 0 0

Then, using the relation, Ŝx = 12 (Ŝ+ − Ŝ− ), we obtained the matrix elements
of the operator and corresponding eigenstates,

x = 1 mx = 0  x = −1
  m m
0 1 0
!  1 1 1
Ŝx = √ 1 0 1 , 1 √  1 1 √ 
2 2 √  0  − 2
0 1 0 2 2 2
1 −1 1

Advanced Quantum Physics

16.1. PROBLEM SET I 201

When placed in a magnetic field, B, the molecules will acquire an energy

µBmz !, where µ is the magnetic moment of the molecule, which in this case
equals twice the magnetic moment of the proton, and mz ! is the eigenvalue of
Ŝz . At t = 0, the molecules enter the magnetic field in the mx = 1 state, after
which their wavefunction evolves with time in the usual way, i.e.
 −iµBt    −iµBt 
e 0 0 1 e√
1 √ 1
ψ(t) = e−iµB Ŝz t/! ψ(0) =  0 0 0  2  =  2 .
2 2
0 0 eiµBt
1 eiµBt

Thus, if µBt = (2n + 1)π, with n an integer, the molecules will be in a pure
mx = −1 state,
0 and none will pass the second filter. The time is given by
t = L/v = L m/2E, where L = 20 mm and m and E are the mass and energy
of the molecules respectively. We thus have
% &1/2
(2n + 1)π! 2E
µ= = 2.84 10−26 JT−1
BL m
and hence the proton magnetic moment is 1.42 10−26 JT−1 .
Note that the result can also be obtained by treating the problem as one of
classical precession. The couple = µB = LΩ, where L = ! is the angular
momentum and Ω the angular frequency of precession. If Ωt = (2n + 1)π, the
molecules have precessed into the mx = −1 state, and the result readily follows.

8. Substituting for the definition of the spin raising and lowering operators using
the Holstein-Primakoff transformation, the commutator is obtained as

%
†
a+1%
&1/2 a #$!" &1/2 % &
1 †
a a a† a a† a
[Ŝ +
, Ŝ −
] = 1 − aa †
1 − − a †
1 − a
2S!2 2S 2S 2S
% & % &
a† a a† a a† a† aa a† a
= 1− + a† a 1 − − a† a + =1− .
2S 2S 2S S
With Ŝ z = !(S −a† a), we obtain the required commutation relation [Ŝ + , Ŝ − ] =
2!Ŝ z .

M (m1 , m2 )
9. For the case -1 = 1, -2 = 2, a table of possible ways of forming each value
3 (1, 2)
of M = m1 + m2 is shown right. The largest value of M is 3, so the largest
2 (1, 1) (0, 2)
value of L must be 3. There must also be a state with M = 2 corresponding
1 (1, 0) (0, 1) (−1, 2)
to L = 3, but we have two states with M = 2. Therefore there must be a
0 (1, −1) (0, 0) (−1, 1)
state with L = 2 as well. We need two states with M = 1, one for each of the
−1 (1, −2) (0, −1) (−1, 0)
L = 3, 2 multiplets, but we actually have three states with M = 1, so there
−2 (0, −2) (−1, 1)
must be an L = 1 state as well. All of the M states are now accounted for.
−3 (−1, −2)
For the case -1 = 3, -2 = 1, we can again for a table (see right). Following the
same logic as before, we see that states with L = 4, 3, 2 just account for all the M (m1 , m2 )
states. 4 (3, 1)
To construct the states explicitly, we start by writing the L = 3 M = 3 state, 3 (3, 0) (2, 1)
since there is only one way of forming M = 3, viz. |3, 3# = |1, 1# ⊗ |2, 2#. We 2 (3, −1) (2, 0) (1, 1)
then operate with the lowering operator L̂− , which is simply the sum of the 1 (2, −1) (1, 0) (0, 1)
lowering operators for the two separate particles. Recalling that: 0 (1, −1) (0, 0) (−1, 1)
0 −1 (0, −1) (−1, 0) (−2, 1)
L̂− |-, m# = -(- + 1) − m(m − 1)!|-, m − 1# ,
√ √ √ −2 (−1, −1) (−2, 0) (−3, 1)
we obtain 6!|3, 2# = 2!|1, 0# ⊗ |2, 2# + 4!|1, 1 ⊗ |2, 1#, where the first −3 (−2, −1) (−3, 0)
term on the right hand side comes from lowering the 0 - = 1 state and the −4 (−3, −1)
second
0 from lowering the - = 2 state. Hence |3, 2# = 1/3!|1, 0# ⊗ |2, 2# +
2/3!|1, 1#⊗|2,
0 1#. The state |2, 2#
0 must be the orthogonal linear combination,
i.e. |2, 2# = 2/3!|1, 0# ⊗ |2, 2# − 1/3!|1, 1# ⊗ |2, 1#. Further states could be
computed in the same way if required.

Advanced Quantum Physics

16.1. PROBLEM SET I 202

10. The commutation relations are given by [Ji , Jj ] = i!.ijk Jk .

(a) First define the eigenstates ψm : Jz ψm = m!ψm . To see if J± ψm is an

eigenstate of Jz , we need to look at Jz J± ψm , which is equal to J± Jz ψm −
[J± , Jz ]ψm . The required commutator is [J± , Jz ] = [Jx , Jz ] ± i[Jy , Jz ],
from the definition of J± . From the basic commutators given at the start,
this is [J± , Jz ] = !) − iJy ± −Jx ) = − ± !J± (if treating ± like a number
is confusing, do this separately for J+ and J− ). Going back to Jz J± ψm ,
we can now write this as J± Jz ψm + ±!J± ψm . The first term is just
J± m!ψm , so this is (m ± 1)!(J± ψm ). Thus, J± ψm is an eigenstate of
Jz , with eigenvalue (m ± 1)!. This establishes the raising and lowering
property of J± .
(b) Two electrons would have a total spin of S = 1 or 0. Adding a third spin
1/2 particle creates total spin S = 3/2 or 1/2 from the S = 1 two-particle
state. The S = 0 two-particle state becomes S = 1/2 only on adding the
third particle, so total S = 3/2 or 1/2 are the only possibilities.
(c) The states with well-defined values of m1 , m2 , and m3 for the z spin
components of all particles are the ‘uncoupled basis’. Where all particles
are ‘spin up’, this state may be written as | ↑↑↑#. This state is also the
mS = 3/2 state of total S = 3/2 (there is no other way to get m1 + m2 +
m3 = 3/2 in the uncoupled basis). We can therefore write |S = 3/2, mS =
3/2# = | ↑↑↑#. To get from here to |S = 3/2, mS = 1/2#, we need to apply
(1) (2) (3)
J− = S− + S− + S− . In other words, the total lowering operator is the
sum of the lowering operator for each separate spin (reasonably enough)
(1) (2) (3)
this follows from the definition of J− and Jx = Sx + Sx + Sx , etc.
Now, we need to use the given normalization result. This says that
0
J− |S = 3/2, mS = 3/2# = 15/4 − 3/4!|S = 3/2, mS = 1/2#
√
= 3!|S = 3/2, mS = 1/2# .

Notice that the total quantum number, J, is the same as the overall spin
quantum
√ number, S in this case. Therefore |S = 3/2, mS = 1/2# =
(1/ 3)J− |S = 3/2, mS = 3/2#. Using 0 the given normalization result
again for a single state, S− |1/2, 1/2# = 3/4 + 1/4!|1/2, −1/2#. This
establishes the required result.

Advanced Quantum Physics

16.2. PROBLEM SET II 203

16.2 Problem Set II

1. Perturbation theory: This question provides a very instructive applica-
tion of approximation methods in quantum mechanics. The first part of the
problem is straightforward and addresses the perturbative series expansion
of the anharmonic oscillator. However, the same problem can be used to
illustrate the failure of perturbation theory. The second part of the problem
demands an application of the WKB method and illustrates the origin of
the limitations of the perturbative scheme.
Briefly summarize how perturbation theory can be used to obtain ap-
proximate values for the energy of a non-degenerate state when an exact
solution of the Schrödinger equation is unavailable.

(a) An anharmonic one-dimensional oscillator for a particle of mass m

has potential V (x) = 12 mω 2 x2 + λx4 , where λ > 0 is small. Using The ground state of the un-
perturbation theory, determine the ground state energy to first or- perturbed oscillator is given by
2
der in λ. Consider how your result can be obtained using the ladder ψ0 (x) = ( mω
π! )
1/4
exp(− mωx
2! ).
operator formalism.
† (b) When λ < 0, the anharmonic oscillator provides an instructive
example illustrating the failure of perturbation theory. No matter
how small is the value of λ, the potential minimum at x = 0 can
only be metastable: For x large enough, the potential eventually You may note that
turns negative providing an escape route for the particle from the ! b
b3
harmonic potential. For this tunneling problem, make use of the dx x(b2 − x2 )1/2 = .
WKB method to estimate (roughly) the tunneling probability and 0 3
thereby elucidate the origin of the failure of the perturbation series
expansion in λ.

2. Perturbation theory: In addition to relativistic corrections, the Hamil-

tonian of the hydrogen atom is also perturbed by the finite range of the
nucleus. The following problem exploits perturbation theory to explore the
scale of such corrections. Hint: You can, and should, sim-
plify the integrals considerably
The fact that the proton is not a point charge influences the energy levels
by noting that the size of the nu-
of the hydrogen atom. This problem may be treated (for simplicity) cleus is much smaller than the
by regarding the proton as a uniformly charged hollow spherical shell atomic Bohr radius, i.e. b " a0 .
of radius b = 5 × 10−16 m. Show that the change in the electrostatic You may" note#that, $
potential energy corresponds to introducing a perturbation ψ2s = 8πa 1
3 1 − 2ar 0 e−r/2a0 ,
0
% & −r/2a0
e2 1 1 ψ2p0 = re
√ cos θ,
32πa50
Ĥ (x) =
(1)
− , r < b,
4π&0 r b ψ2p±1 = re
√
−r/2a0
e±iφ sin θ.
64πa50
into the normal Schrödinger equation for the hydrogen atom. Using first
order perturbation theory, estimate the energy shifts of the hydrogen 2s
and 2p states and comment on your findings. Suggest why measurement
of such energy shifts is not a good way of studying the proton charge
distribution.

3. Perturbation Theory:This problem shows how perturbation theory may

be used to estimate the polarizibility of the hydrogen atom in its ground
state. (The induced dipole moment in an applied electric field E is α&0 E
where α is the polarizibility.)

Advanced Quantum Physics

16.2. PROBLEM SET II 204

Working to second order in field, E, show that induced polarization of

2 ' |#k|z|0$|2
the ground state |0% is given by α = 2e !0 k"=0 Ek −E0 , where Ek is
the unperturbed energy of state |k%. Show that the same result may
be obtained from the perturbed wavefunction to first order in E and
evaluating the expectation value of the induced electric dipole moment. To derive the matrix element,
&0|z 2 |0%, you will need the
Evaluation of α is tedious, but a useful upper bound may be obtained by
ground state of the hydrogen
noting that Ek ≥ E1 , where E1 is the energy of the first excited. Using atom, |0% = ( πa1 3 )1/2 e−r/a0 .
64πa3
this result, show that α ≤ 3 0 . Compare this with the experimental 0

value of α = 8.5 × 10−30 m3 .

Variational method:The following three problems involve straightfor-

ward applications of the variational state analysis.
4. Give an account of the variational method for estimating the ground
state energy of a quantum mechanical system. Explain how the method
may also be applied to excited states.
Use a trial wavefunction of the form,
(
A(a2 − x2 ) −a < x < a
ψ(x) = ,
0 otherwise
to place an upper bound on the ground state energy of the one-dimensional
harmonic oscillator with potential V (x) = mω 2 x2 /2 where m is the mass
of the particle and ω the oscillator frequency. Compare your answer with
the exact result, and comment.

5. By taking a trial wavefunction proportional to exp(−βr) where β is a

variational parameter, obtain an upper limit for the ground state energy
of the H atom in terms of atomic constants. Comment on your result.

6. (a) E1 and E2 are the ground state energies of a particle moving in Hint: Use the wavefunction of a
attractive potentials V1 (r) and V2 (r). Using the variational method, particle moving in V2 (r) as a trial
show that E1 ≤ E2 if V1 (r) ≤ V2 (r). wavefunction for potential V1 (r).
(b) Consider a particle moving in a one-dimensional attractive potential
V (x), i.e. a potential such that V (x) ≤ 0, for all x and V (x) →
0, as |x| → ∞. Use the variational principle with trial function
A exp(−λx2 ) to show that the upper bound on the ground state
energy is negative, and hence that for any such potential at least
one bound state must exist.

7. The following question addresses the constraints imposed by particle in-

distinguishability on the allowed spin and spatial states of a two-particle
quantum mechanical system.
Discuss the special considerations which apply to systems of indistin-
guishable particles in quantum mechanics, giving examples where they
lead to observable consequences.
Two non-interacting particles of mass m move in one dimension, their
positions given by x1 and x2 . The potential is given by
(
0 0<x<L
V (x) = .
∞ otherwise

Advanced Quantum Physics

16.2. PROBLEM SET II 205

Show that the energy of the system is of the form E = (n21 + n22 )ε where
n1 and n2 are integers and find an expression for ε. Consider the state
with E = 5ε for each of the following three cases:

(a) spin-zero particles;

(b) spin-1/2 particles in a spin singlet state;
(c) spin-1/2 particles in a spin triplet state.

In each case, what is the symmetry of the spin and spatial parts of the
wavefunction? Hence write down the spatial wavefunction, and sketch
the probability density |ψ(x1 , x2 )|2 in the (x1 , x2 ) plane.
Describe qualitatively how the energies of these states would change if
the particles carried electric charge and hence interacted with each other
(an example of the exchange interaction).

8. Together with the constraints imposed by particle indistingishability, a sec-

ond feature of many-body problem in quantum mechanics is their typical
analytical intractability! In the vast majority of interacting problems, some
approximation is necessary. The following question involves an application
of perturbation theory to a two particle system.
Two identical spin-zero bosons are placed in a one-dimensional square
potential well with infinitely high walls; V = 0 for 0 < x < L, otherwise
V = ∞. The normalized single-particle energy eigenstates are given by
un = (2/L)1/2 sin(nπx/L).

(a) Find the wavefunctions and energies for the ground state and the
first two excited states of the system.
(b) Suppose that the two bosons interact with each other through the
perturbative “contact interaction”,

Ĥ % (x1 , x2 ) = −V0 Lδ(x1 − x2 ) .

Compute the the ground state energy to first order in V0 .

Advanced Quantum Physics

16.2. PROBLEM SET II 202

Answers: Problem set II

1. (a) For λ > 0, the first order shift in ground state energy is given by
! ∞ " mω #1/2 ! ∞ 2 3!2 λ
∆E0 = ψ0∗ λx4 ψ0 dx = dxλx4 e−mωx /! = .
−∞ π! −∞ 4m2 ω 2
$
!
Alternatively, using the identity x = 2mω (a + a† ), we have
% &2
!
∆E0 = λ !0|(a + a† )4 |0"
2mω
λ!2 3!2 λ
= !0|(a (a
2 † 2
) + aa †
aa †
+ a† 2 †
a a )|0" = .
4m2 ω 2 4m2 ω 2
(b) For λ < 0, the situation becomes more subtle. The potential now takes the
form of an upturned double well potential with a metastable minimum
at zero. Here, as we will see, conventional perturbative approaches fail.
However, we can straightforwardly implement the WKB approach to com-
pute the tunneling amplitude from the well created by the perturbation
using the relation,
!
1 b '
t∼e ,−S
S= dx 2m(V (x) − E0 ) .
! a
To implement the WKB method, we have to first identify the classical
turning points.
If λ is small in magnitude, the ground state energy of the unperturbed
oscillator is neglible as compared to the barrier height and we may set
E0 = !ω/2 % 0. The classical turning points are determined by the
equation E0 = V (x) = 12 mω 2 x2 − λx4 . The latter has the solution at
x = a % 0 (with more care, we can show ' that it is simply the
' turning
point of the harmonic oscillator, x0 = !/mω) and x = b mω 2 /2λ.
(The reflection about x = 0 also gives another set of solutions.) We
therefore obtain
√ !
2mλ b 2m2 ω 3
S% dx x(b2 − x2 )1/2 = ,
! 3!λ
(0 )* +
b3 /3

which leads to the transmission probability

, -
4m2 ω 3
|t| ∼ exp −
2
.
3!λ

This result exposes the problem with perturbation theory: it assumes that
the ground state energy is an analytic function of λ for some sufficiently
small region around λ = 0. However, this result shows that the true
ground state solution has an essential singularity in λ and the radius of
convergence of the perturbation theory vanishes.

2
2. For a point-like nucleas, the hydrogen atom has a potential V (r) = − 4π#e
0r
. A
hollow spherical shell will have the same potential for r > b, but V (r) = V (b)
for r < b, by Gauss theorem, and thus its effect can be regarded as adding a
perturbation,
% &
e2 1 1
Ĥ (1) = − ,
4π%0 r b
to the Hamiltonian for r < b, and zero for r > b. For the 2s wavefunction, the
energy shift induced by the perturbation is
! b % &% &2
1 e2 1 1 r
∆E = !ψ|Ĥ |ψ" =
(1)
4πr dr
2
− 1− e−r/a0 .
8πa30 4π%0 0 r b 2a0

Advanced Quantum Physics

16.2. PROBLEM SET II 203

Since b ' a0 , the terms involving r/a0 are negligible in the region of integration,
so we can simplify the integral to
! b % &
e2 1 1 b2 e2
∆E = r 2
dr − = R ∞ , R ∞ = .
8π%0 a30 0 r b 6a20 8π%0 a0
Likewise for the 2p0 wavefunction, making the same approximation, we obtain
! b % &! π
e2 1 1 b4
∆E = r 4
− dθ2π sin θ cos 2
θ = R∞ .
128π 2 %0 a0 0
5 r b 0 240a40
Both energy shifts are very small, but that for the 2p state is much smaller,
because the 2p wavefunction vanishes at the origin.
This is not a good method to explore the nucleus because other effects, such
as spin-orbit interaction and other relativistic corrections would swamp the
nuclear size effect. It is more effective for heavy atoms, with larger nuclei and
smaller Bohr radii, and especially for “muonic” atoms, where the greater mass
of the muon again reduces the Bohr radius.

3. If, without loss of generality, we take the field to lie along z, the perturbation is
given by Ĥ $ = −eEz. At first order in perturbation theory, ∆E = −!0|eEz|0"
vanishes since the ground state of the hydrogen atom |0" is an eigenstate parity.
The leading contribution to ∆E is therefore the second order term ∆E =
. |&k|eEz|0'|2
k%=0 E0 −Ek . If the induced dipole moment is d = α%0 E, its energy of
interaction with the electric field is given by ∆E = − 12 d · E = − 12 α%0 E 2 . So,
by comparing with our perturbation theory result we obtain the required result.
An alternative derivation of this result starts from the first order perturbation
.
theory expression for the perturbed wavefunction: |ψ" = |0" + k%=0 ck |k",
where ck = &k|−eEz|0'
E0 −Ek . The dipole moment operator for the electron is ez, and
its expectation value in this state is (neglecting small terms of order (c2k )),
/
!ψ|ez|ψ" = !0|ez|0" + [ck !0|ez|k" + c∗k !k|ez|0"] +O(c2k ) = α%0 E
( )* +
k%=0
=0 ( )* +
P |"k|ez|0#|2
2E k!=0 Ek −E0

from which the value of α follows as before.

Since Ek ≥ E1 for all k, we obtain
2e2 / |!k|z|0"|2 2e2 / !0|z|k"!k|z|0" 2e2 !0|z 2 |0"
α≤ = = ,
%0 E1 − E0 %0 E 1 − E0 %0 E1 − E0
k%=0 k%=0
.
where we have used the completeness relation I = k |k"!k|. Note that the
sum now includes the k = 0 term. Using the explicit form for the Hydrogen
ground state, |0" = ( πa1 3 )1/2 e−r/a0 , we evaluate the matrix element,
0

! π ! ∞
!0|z 2 |0" = !0|r2 cos2 θ|0" = 2π sin θ cos2 θdθ r2 drr2 e−2r/a0 = a20 .
0 0

e2
We also need the energy difference, E1 − E0 = (1 − 14 )R∞ = 3
4 8π#0 a0 from
64πa30
which we obtain α ≤ 3 = 9.9 × 10 −30
m , a figure that is not too far from
3

experiment.

4. From
0 ∞ the trial wavefunction,
0a we can obtained A from the normalization, 1 =
−∞
|ψ|2 dx = A2 −a (x4 − 2a2 x2 + a4 )dx = 16 15 A a . Moreover, using the
2 5

identity,
% & , 2 -
!2 2 1 ! 1
Ĥψ = − ∂ + mω x ψ = A
2 2
+ mω (a x − x )
2 2 2 4
2m x 2 m 2

Advanced Quantum Physics

16.2. PROBLEM SET II 204

the expectation value of the Hamiltonian is given by

! a , 2 - , -
! 1 15 2!2 4mω 2 a2
!ψ|Ĥ|ψ" = A2 (a2 − x2 ) + mω 2 (a2 x2 − x4 ) dx = + .
−a m 2 8 3ma2 105
1/2 !
Minimising with respect to a we obtain a2 = ( 35 2 ) mω . Substituting this
value of a into our expression for$
!ψ|Ĥ|ψ", we obtain the upper bound on the
ground state energy, !ψ|Ĥ|ψ" = 14 5
!ω = 0.598!ω, which is greater than the
true ground state energy (!ω/2) as expected.

0∞ 4πA2 β3
5. From the normalization, 1 = A2 0
4πr2 e−2βr dr = 4β 3 ⇒ A2 = π . From
2β −βr
the identity ∇2 ψ = r12 ∂r (r2 ∂r ψ) = r12 ∂r (−βr2 e−βr ) = β 2 e−βr − r e , we
have
! ∞ , % & -
!2 2β −2βr e2 −2βr
!ψ|Ĥ|ψ" = A2 4πr2 dr − β 2 e−2βr − e − e
0 2m r 4π%0 r
!2 β 2 e2 β
= − .
2m 4π%0
me2
Minimising with respect to β we obtain β = 4π#0 !2 = a−1
0 , which is the inverse
e2 2
of the Bohr radius and thus !ψ|Ĥ|ψ" = m
− 2!2 ( 4π# )
= −13.6 eV. This is the
0
correct value for the ground state energy of the Hydrogen atom, as expected,
because we chose the correct functional form for the trial function.

6. (a) Suppose that the two Hamiltonians are Ĥ1 and Ĥ2 with ground state
wavefunctions ψ1 and ψ2 , i.e. Ĥ1 ψ1 = E1 ψ1 , and Ĥ2 ψ2 = E2 ψ2 . Given
that V1 ≤ V2 , we have Ĥ1 = Ĥ2 − V2 (r) + V1 (r) = Ĥ2 + ∆V (r). From the
variational principle,
E1 ≤ !ψ2 |Ĥ1 |ψ2 " = !ψ2 |Ĥ2 |ψ2 " − !ψ2 |∆V |ψ2 " = E2 + !ψ2 |∆V |ψ2 " ≤ E2 ,
where the last inequality follows because ∆V (r) ≤ 0. Thus E2 ≥ E1 .
2
!
(b) The Hamiltonian is given by Ĥ = − 2m ∂x2 + V (x), and the normalized trial
1/4 −λx2
function is given by ψ =$ (2λ/π) e . Using standard integrals, we
!2
0
2λ ∞ 2
!2
obtain !ψ|Ĥ|ψ" = 2m λ + π −∞ dxV (x)e−2λx = 2m λ + I. Minimsing
with respect to λ, we obtain,
1 !
!2 I I 2λ 2
0= + + + V (x)(−2x2 )e−2λx ,
2m 2λ 2λ π
where the second term arises from differentiating the normalization in I,
and the third term from differentiating the integrand. This is an implicit
equation for λ and if we solve for I and substitute into the equation from
above, we obtain
1 !
!2 !2 2λ 2
!ψ|Ĥ|ψ" = λ+I =− λ + 2λ dxV (x)(2x2 )e−2λx .
2m 2m π
This is our upper bound on the ground state energy, and since V (x) ≤ 0,
both terms are manifestly negative. Hence the ground state energy is
negative, and at least one bound state must exist.

7. A single particle in the potential well has the (unnormalized) wavefunction and
!2 π 2 2
energy, ψn (x) = sin(nπx/L) and E = 2mL 2n ≡ %n2 . The wavefunction for a
system of two identical particles must be either symmetric or antisymmetric,
i.e.
ψ(x1 , x2 ) = sin(n1 πx1 /L) sin(n2 πx2 /L) ± sin(n2 πx1 /L) sin(n1 πx2 /L) ,
with energy (n21 + n22 )%. If E = 5%, we must have n1 = 1, and n2 = 2 (or vice
versa).

Advanced Quantum Physics

16.2. PROBLEM SET II 205

(a) Spin-zero particles are bosons and must have a symmetric wavefunction,

ψ(x1 , x2 ) = sin(πx1 /L) sin(2πx2 /L) + sin(2πx1 /L) sin(πx2 /L)

= 2 sin(πx1 /L) sin(πx2 /L) [cos(πx1 /L) + cos(πx2 /L)] .

Clearly, this has zeros when x1 = 0, L, when x2 = 0, L, and when

x1 + x2 = L.
(b) Spin 1/2 particles are fermions and must have an antisymmetric wave-
function. In the singlet case, the spin wavefunction is antisymmetric, and Symmetric wavefunction
hence the spatial wavefunction is symmetric, just as in (a).
(c) In the triplet case, the spin wavefunction is symmetric, and hence the
spatial wavefunction must be antisymmetric, i.e.

ψ(x1 , x2 ) = sin(πx1 /L) sin(2πx2 /L) − sin(2πx1 /L) sin(πx2 /L)

2 sin(πx1 /L) sin(πx2 /L) [cos(πx1 /L) − cos(πx2 /L)] .

Clearly, this has zeros when x1 = 0, L, when x2 = 0, L, and when x1 = x2 .

If the particles were charged, they would repel each other through the
Coulomb interaction. Therefore, in the spin 1/2 case, the triplet state Antisymmetric wavefunction
would have the lower energy, because the particles tend to be further
apart. This is an example of the exchange interaction, and is a simplified
model of what happens in the Helium atom.

2 2
π !
8. For the single-particle states, E = n2 8ma 2 = %n
2
Since this well is not centred
on zero, the single-particle eigenstates are all just proportional to sin(nπx/2a) ≡
|n".

(a) If we write the two-particle states as |n1 , n2 ", the ground state is |1, 1"
(E = 2%). The first excited states are |2, 1" and |1, 2" (E = 5%). The second
excited state is |2, 2" (E = 8%). The overall wavefunction needs to be sym-
metric for bosons, which |1, 1" and |2, 2" are already. These therefore pair
with a symmetric spin wavefunction, which is always possible, whether or
not the bosons have spin zero. For the first excited state, both symmetric
√
and antisymmetric combinations are possible: (|2, 1" ± |1, 2")/ 2; these
would need to pair with spin wavefunctions that are respectively symmet-
ric and antisymmetric. If S > 0, both are possible; if S = 0, only the
symmetric space state is allowed.
The (normalized) ground state wavefunction is given by
1
ψ(x1 , x2 ) = !x1 , x2 |1, 1" = sin(πx1 /2a) sin(πx2 /2a) .
a

(b) According to first order perturbation theory, the change in the ground state
energy caused by Ĥ $ is given by ∆E = !Ĥ $ ", where0 0 the expectation value
involves the unperturbed
00 eigenfunctions, ∆E = ψ ∗
(x
0 1 , x2 )Ĥ ψ(x1 , x2 )dx1 dx2 .
$

Using the identity, f (x1 , x2 )δ(x1 − x2 )dx1 dx2 = f (x1 , x2 )dx1 , for
any function f , we have
! ! ! 1
2V0 2a 4
∆E = −2aV0 |ψ(x, x)| dx = −2
sin (πx/2a) = −4V0 sin4 (πy)dy .
a 0 0

The sin4 (πy) looks nasty, but written as sin2 (πy)×sin2 (πy), with sin2 (πy) =
(1 − cos(2πy))/2, it is easily evaluated and gives ∆E = −3V0 /2.

Advanced Quantum Physics

16.3. PROBLEM SET III 210

16.3 Problem Set III

1. Atomic structure: The following question begins with a recapitulation of the
leading relativistic corrections to the Schrödinger Hamiltonian of hydrogen-
like atoms.
Explain the physical origin of the following terms in the Hamiltonian for
one-electron atoms:
(p̂2 )2
Ĥ1 = −
8m3 c2
1 (∂r V )
Ĥ2 = L̂ · Ŝ
2m2 c2 r
Ze2 !2
Ĥ3 = 4πδ (3) (r) .
4π#0 8(mc)2

Here m denotes the electron mass, V the electrostatic potential generated

by the nucleus, and Z the atomic number.
The hydrogenic radial wavefunctions have the form, Explicit evaluation of numerical
factors is not required.
! "3/2 ! " # $
Z Zr Zr
ψn! (r) = Gn! exp − ,
a0 a0 na0

where a0 denotes the Bohr radius and Gn! is a polynomial function of its
argument. Show that the expectation values of the energies associated
with the three terms listed above all have the same dependence on Z.
(Part IB Advanced Physics 1993.)

2. Atomic structure: The following problem addresses the electron configura-

tion of multi-electron atoms. In completing this question, you should remind
yourself of the physical origin of the Hund’s rules.
Determine the possible spectroscopic terms, 2S+1 LJ , for each of the fol-
lowing electron configurations: (2s)(3p), (2p)2 , (3d)2 , (3d)10 , and (3d)9 .
Using Hund’s rules, determine the angular momentum quantum numbers
of the ground state of Sm, which has electron configuration (4f )6 .

3. Atomic structure: The following problem addresses the interplay between

LS and jj coupling.
The ground state of Ge has the configuration (4p)2 and spectroscopic
term 3 P0 . Explain the meaning of this notation and state the assump-
tions about atomic structure on which it is based.
Derive the allowed states of a (3p)1 (4s)1 configuration in (i) LS coupling
and (ii) jj coupling, sketching an energy level diagram in each case.
Explain the interactions which give rise to the various energy splittings.
For a certain element, the energy levels given right, which are specified
relative to the ground state, are known to belong to a (6p)1 (7s)1 config- (a) 4.334 eV
uration. Deduce what you can about the quantum numbers appropriate (b) 4.375 eV
to each energy level, given their relative magnitude and the fact that (c) 5.975 eV
only levels (b) and (d) decay to the J = 0 ground state by electric dipole
(d) 6.130 eV
transitions.

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16.3. PROBLEM SET III 211

4. † Atomic spectra: By drawing upon your knowledge about the properties

of multielectron atoms, the following problem requires the decipher of the
atomic spectra of sodium.
The three groups of lines shown right, whose frequencies are given in I Doublets with decreasing dou-
units of 1015 Hz, are observed in the emission spectrum of atomic sodium. blet splitting:
By identifying the spectral lines with specific states of sodium, make an 0.50899 0.90782 1.05086 1.11848
index of the associated transitions. In doing so, you will find it helpful to 0.50847 0.90765 1.05079 1.11845
address the following questions: (i) What are the appropriate quantum
numbers for the ground state and low energy excited states of sodium? II Doublets with constant dou-
blet splitting:
(ii) Which energy levels are split by the spin-orbit interaction? (iii) How
0.26340 0.48713 0.58225 0.63142
(qualitatively) does the spin-orbit coupling depend on n? (iv) Which
0.26288 0.48662 0.58174 0.63090
transitions are allowed by the dipole selection rules?
Draw an energy level diagram, taking the (3s) state as the zero of energy, III Triplets, with two lines some-
and answer the following questions: times unresolved:
0.36635 0.52756 0.60207 0.64267
(a) What is the energy difference between the (5p) J = 3/2 and J = 1/2 0.365833 0.52704 0.60165 0.64215
states in sodium? 0.365831

(b) Estimate the first ionization energy of sodium.

(c) What are the relative importances of the &-dependence of the electron-
electron energy, and the j-dependence of the spin-orbit energy in
the n = 3 and n = 6 shells?

5. Zeeman effect: This problem involves the study of the infleunce of a weak
magnetic field on the spectrum of a multielectron atom. Here we are in-
terested in exploring the interplay between LS coupling and the influence of
the external field.
For an atom characterised by LS coupling, and subject to a weak uniform
magnetic field, derive the expression for the Landé g-factor,

J(J + 1) − L(L + 1) + S(S + 1)

g =1+ .
2J(J + 1)

In a Zeeman experiment, the 3 S1 →3 P1 emission of an ensemble of such

atoms is observed in the presence of a weak magnetic field B. Describe
the resulting Zeeman structure of the atomic levels, and indicate which
transitions amongst the split levels are allowed in an electric dipole tran-
sition. Sketch the form of the line spectrum seen in some general direc-
tion before and after the field is applied. Label, in units of µB B where
µB is the Bohr magneton, the positions of the components relative to
the energy of the unperturbed transition. Hint: Consider how the elec-
If the emission is viewed perpendicular to the direction of the magnetic tric field couples to the elec-
field, how many lines will be observed and what polarization states will tric dipole and how this trans-
they have? lates to constraints on the al-
lowed change in MJ .

6. Atomic structure: As well as the interaction between the spin and orbital
degrees of freedom of the electron which follow from the relativistic cor-
rections, the magnetic field generated by the nuclear magnetic momentum
also lead to corrections to the electron Hamiltonian. These corrections are
known as hyperfine coupling. The following problem involves exploring the

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16.3. PROBLEM SET III 212

evolution of the hyperfine spectrum of the hydrogen atom in the presence

of a weak magnetic field.
The magnetic part of the Hamiltonian for a hydrogen atom in the 1s
state, in the presence of a constant magnetic field B along the z axis,
may be cast in the form
% &
Ĥ = B µe σz(e) + µp σz(p) + W σ (e) · σ (p) ,

where the superscripts e and p refer to the electron and proton, the vector
components of σ are the Pauli spin operators, µe,p are the respective
magnetic dipole moments, and W is a constant.

(i) Explain the physical origin of each term in the Hamiltonian.

(ii) Using as a basis the states | ↑e $ ⊗ | ↑p $, | ↑e $ ⊗ | ↓p $, | ↓e $ ⊗ | ↑p $,
| ↓e $ ⊗ | ↓p $, and neglecting the small term in µp , show that the Ĥ
may be represented by the matrix
 
b+W 0 0 0
 0 b−W 2W 0 
 ,
 0 2W −b − W 0 
0 0 0 −b + W

where b = µB B. (Explain why µp is small in comparison to µe .)

(iii) Determine the energy levels and sketch their evolution as a function
of B, labelling them with as much information as possible about
the total angular momenta of the states.

7. Molecular structure: This problem concerns the application of the LCAO

method to molecular bonding in the H+
3 ion.
Explain what is meant by the Born-Oppenheimer approximation and
discuss how molecular wavefunctions can be formed within this approx-
imation by using the Linear Combination of Atomic Orbitals (LCAO).
The H+ 3 ion exists as an isosceles triangle (distance d12 = d23 '= d31 ),
with the internal bond angle 60◦ ≤ θ ≤ 180◦ . Treating this ion in the
LCAO approximation, introducing the 1s basis state wavefunctions, |ψi $
for the ith atom, show that the electron energy levels are solutions of the
secular equation
- -
- α−E β γβ --
-
- β α−E β - = 0,
- -
- γβ β α−E -

where α = )ψ1 |Ĥ|ψ1 $ = )ψ2 |Ĥ|ψ2 $ = )ψ3 |Ĥ|ψ3 $, β = )ψ1 |Ĥ|ψ2 $ =

)ψ2 |Ĥ|ψ3 $, and βγ = )ψ1 |Ĥ|ψ3 $, where Ĥ is the Hamiltonian for the ion.
In this case, as an approximation, you may ignore the overlap integrals,
)ψi |ψj $. Find the energy levels and sketch them in the range 0 ≤ γ ≤ 1.
Show that the ground state must be a spin singlet, and predict which
value of γ should be most stable. Qualitatively, how would you expect
γ to vary with θ, and hence, what would you expect to be the value of
θ in the most stable configuration? [Note that the matrix element β is
negative.] (Part II 1998)

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16.3. PROBLEM SET III 213

Figure 16.1: Infra-red rotation-vibration band spectrum of HCl measured in Hz.

8. Molecular structure: This problem explores the relative influence of valance

bonding in H2 .
In the pure valence bonding approximation, the electronic ground state
wavefunction of the H2 molecule is given by

ψ VB = C[ψa (r1 )ψb (r2 ) + ψb (r1 )ψa (r2 )] ,

where ψa and ψb are the (real) ground state wavefunctions of the two
hydrogen atoms.

(i) Express the

. normalization constant C in terms of the overlap inte-
gral S = d3 r ψa ψb .
(ii) Express ψ VB in terms of the molecular bonding and antibonding
orbitals, (σg (1), σg (2)) and (σu∗ (1), σu∗ (2)), defined in lectures.
(iii) Hence find a second molecular state ψ⊥ orthogonal to ψ VB and
interpret it in terms of covalent and ionic components.
(iv) Use the result S = (1 + ρ + ρ2 /3)e−ρ with ρ = R/a0 * 1.6 to
estimate the configuration mixing (i.e. the relative contributions of
the VB and ionic bond) in H2 .

9. Molecular spectra: This question addresses the features of the rotation-

vibration spectra of the diatomic molecule HCl. It also provides an exercise
in the application of selection rules to radiative transitions.
Explain the following features of the rotation-vibration absorption spec-
trum of HCl shown in Fig. 16.1: (i) the missing peak at the centre, (ii)
the double peak structure, (iii) the line spacing and why it is uneven,
(iv) the intensity as a function of wave number. Determine the values of
as many molecular parameters as you can from the spectrum.

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16.3. PROBLEM SET III 211

Answers: Problem set III

! !
1. (a) Using the relation, !ψ| Ĥ1 |ψ" ∼ r2 drψ ∗ p̂4 ψ ∼ r2 dr|∇2 ψ|2 , consider
the change of variables u = Zr/a0 . Since ∂x = aZ0 ∂ux , ∇2 = ( aZ0 )2 ∇2u and
" # $4 % %2
u2 du Z % 2 %
!ψ| Ĥ1 |ψ" ∼ Z 3
%∇u G(u)e−u/n % ∼ Z 4 .
Z3 a0
2 2
(b) For the Coulomb interaction, V = − 4π"
Ze
0r
, so ∂r V = 4π"
Ze
0r
2 and

" " # $
Z dr Zr
!ψ| Ĥ2 |ψ" ∼ r2 dr|ψ|2 3 ∼ Z 4 Gn# e−2Zr/na0 .
r r a0
The integral is independent of Z, as can easily be seen by making a change
of variables u = Zr/a0 , and hence !ψ| Ĥ2 |ψ" ∝ Z 4 .
(c) Making the usual substitution u = Zr/a0 , we have δ 3 (r) = ( aZ0 )3 δ 3 (u) and
thus the expectation value of this term in the Hamiltonian is
" " 2 # $3 # $3
u du Z Z
!ψ| Ĥ3 |ψ" ∼ r dr Zδ (r)|ψ| ∼
2 (3) 2
Z δ (u)
3
G2 (u)e−2u/n ,
Z3 a0 a0
which is proportional to Z 4 again.

2. (2s)(3p) The allowed values of L and S are S = 0, 1, L = 1. Since the electrons

are inequivalent, all combinations of L and S are allowed, i.e. 1 P1 , 3 P0,1,2 .
(2p) Since the electrons are equivalent, we may take S = 0 (antisymmetric)
2

with symmetric spatial wavefunction L = 0, 2, or alternatively S = 1

(symmetric) with antisymmetric spatial wavefunction L = 1, i.e. 1 S0 ,
1
D2 , 3 P0,1,2 .
(3d)2 Since the electrons are equivalent, we may take S = 0 (antisymmetric)
with symmetric spatial wavefunction L = 0, 2, 4, or alternatively S = 1
(symmetric) with antisymmetric spatial wavefunction L = 1, 3, i.e. 1 S0 ,
1
D2 , 1 G4 , 3 P0,1,2 , 3 F2,3,4 .
(3d)10 This is a completely filled shell, so L = S = J = 0, i.e. 1 S0 .
(3d)9 The shell has just one unoccupied state, so the values of L, S and J are
just those for a single electron in the shell, i.e. L = 2, S = 1/2 and the
terms are 2 D3/2,5/2 .
(4f )6 Applying Hund’s first rule, the maximum S = 3. Being maximal, this
spin state is symmetric with respect to interchange of electrons, so the
spatial state must be totally antisymmetric. Hence the six electrons must
occupy six different m# values out of the seven (2$ + 1) available. As
a result, the ML of the atom can take one of seven possible values,
ML = ±3, ±2, ±1, 0. As a result, we can deduce that L = 3 is the only
possibility. The shell is less than half full, so Hund’s third rule requires
J = |L − S| = 0, i.e. 7 F0 .

3. The 3 P0 notation signifies the total angular momentum quantum numbers in

the form 2S+1 LJ , hence S = 1, L = 1 and J = 0 in this case. The notation
implies that the LS coupling approximation is appropriate, so that L and S are
good quantum numbers, which will be valid if the residual Coulomb interaction
is much greater than the spin-orbit interaction.
Considering the (3p)1 (4s)1 configuration:

(i) In LS coupling, the allowed values of S and L are S = 0, 1 and L = 1.

According to Hund’s first rule, S = 1 lies lower in energy. The S = 1,
L = 1 state can take three values of J = 0, 1, 2, which are split by the
spin-orbit interaction, with J = 0 lying lowest in energy by Hund’s rules.
The energy levels therefore form a triplet 3 P0,1,2 and a higher lying singlet
1
P1 .

Advanced Quantum Physics

16.3. PROBLEM SET III 212

(ii) In jj coupling, the spin-orbit interaction makes a larger contribution that

the Coulomb term. In this scheme, we must first find the j values for
the two electrons, i.e. j = 1/2, 3/2 for the 3p state and j = 1/2 for
the 4s. These j values will be separated by the spin-orbit interaction.
The smaller Coulomb term will then differentiate between the different
values of J which can be formed by combining the values of j, giving the
following terms,

(j1 , j2 )J = (1/2, 1/2)0,1 , (3/2, 1/2)2,1 .

The states thus form two doublets in this case.

The given energy levels clearly form two doublets (a,b) and (c,d), so the jj
coupling scheme is the better approximation in this case. The electric dipole
selection rules (∆J = ±1, 0; but 0 → 0 forbidden) tell us than only the J = 1
levels can decay to the ground state. We also expect the (1/2, 1/2) level to
lie lower, since !L̂ · Ŝ" ∝ (J(J + 1) − L(L + 1) − S(S + 1)), so this suffices to
identify the levels: (a) is (1/2, 1/2)0 ; (b) is (1/2, 1/2)1 ; (c) is (3/2, 1/2)2 ; (d) is
(3/2, 1/2)1 .

4. Firstly, in answer to the introductory questions:

(i) As an alkali atom, sodium has a single electron outside closed shells.
The low energy excited states involve excitation of this electron. The
appropriate quantum numbers are $, s and j (the quantum numbers for
the whole atom being the same as for the unpaired electron). The al-
lowed states for the electron are [3s(ground state), 3p, 3d], [4s, 4p, 4d, 4f ],
[5s, 5p, 5d, 5f, 5g], etc.
(ii) The spin-orbit interaction splits each level into a doublet according to
j = $±1/2, except for the s-states for which j = 1/2 is the only possibility.
(iii) The strength of the spin-orbit interaction decreases with n, since the
electrons in higher energy levels experience a smaller magnetic field as
the nucleus is better screened.
(iv) Finally, the dipole selection rules require ∆J = ±1, 0, parity change, and
∆$ = ±1.

Since the ns states are singlets with term 2S1/2 while the np states are doublets
with terms 2P3/2,1/2 , we can deduce that all the doublets must involve s ↔ p
type transitions. Since those in group II involve the same doublet spacing, they
must all involve the same p state. They are therefore likely to involve 4s → 3p,
5s → 3p, 6s → 3p and 7s → 3p transitions respectively.
By contrast, those in group I are likely to involve p states decaying to the same
s state. Noting that the first one has the same splitting as group II, we can
deduce that the they are likely to involve 3p → 3s, 4p → 3s, 5p → 3s and
6p → 3s transitions respectively, with the spin-orbit splitting decreasing with
n as expected.
The nd states have terms 2D5/2,3/2 . However, since the selection rules prohibit The Grotrian diagram for
transitions between J = 5/2 and J = 1/2, we can deduce that the transitions sodium showing (some) of
between d ↔ p states must involve triplets, as observed in group III. Since the the dipole allowed transitions.
splittings are the same as in group II, we can deduce that 3p is involved again. The two sodium D-lines are
They must be 3d → 3p, 4d → 3p, 5d → 3p and 6d → 3p transitions respectively. emphasized.
We can compare these predictions with the diagram (right) showing the spectra
of sodium (known as a Grotrian diagram).

(a) The 5p5/2 and 5p3/2 states are involved in the transitions of frequency
1.05086 and 1.05079 × 1015 Hz, which differ by 7 × 1010 Hz. The energy
splitting is thus 7 × 1010 h = 4.6 × 10−23 J = 0.29 meV.

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16.3. PROBLEM SET III 213

(b) We expect the sodium energy levels to converge to the hydrogen levels
for large n, and thus to scale like 1/n2 . To test this, note that the ratio
of the energy differences (6s − 5s)/(7s − 6s) = 1.9, compared with the
expected ratio ( 25
1 1
− 36 )/( 36
1 1
− 49 ) = 1.65, which is not too bad. The energy
difference between the 7s state and the ionisation energy may be estimated
as the energy difference between 7s and 6s (Planck’s constant h times
0.049×1015 Hz) times ( 49 1
−∞ 1
)/( 36
1 1
− 49 ), which yields h×0.135×1015 Hz.
We add this to the energy difference between 7s and 3s, inferred fron the
sum of the 0.63142 × 1015 Hz (7s → 3p) and 0.50899 × 1015 Hz (3p → 3s)
transitions to obtain h × 1.27 × 1015 Hz, i.e. 5.2 eV. You could use other
states instead in a similar way.
(c) The spin-orbit energy in the p-states can be estimated from the splittings
of the corresponding doublets in group I. The Coulomb effect is given by
the difference between the p- and s-levels for a given n. The ratios in the
n = 3 and n = 6 cases are:
spin − orbit 0.00052
n=3: = = 1.02 10−3
coulomb 0.51
spin − orbit 0.00003
n=6: = = 1.07 10−3
coulomb 0.028
i.e. both effects decrease with n at about equal rates.

5. The derivation of the Landé g-factor is standard bookwork. The 3 S1 level

has g = 2 and 3 P1 level has g = 3/2. Bearing in mind the selection rules,
∆MJ = ±1, 0, the shifts in the energy levels are given by,
 
 MJ
 ∆E 
 MJ ∆E
 
1 2µB B 1 3
µB B
3
S1 3
P1 2

 0 0 
 0 0 MJ ∆E
 
−1 −2µB B −1 − 32 µB B 1→1 + 12 µB B
1→0 +2µB B
and thus the shifts in the energies of the allowed transitions are as given right.
0→1 − 32 µB B
The line therefore splits into seven components.
0→0 0
Viewing perpendicular to the magnetic field, all seven lines will be seen. The 0 → −1 + 32 µB B
∆MJ = 0 lines corespond to dipoles parallel to the field, and thus the light will −1 → 0 −2µB B
be plane polarised in the direction of the field; these will have energy shifts of −1 → −1 − 12 µB B
± 21 µB B and zero. The ∆MJ = ±1 lines corespond to dipoles perpendicular to
the field, and thus the light will be plane polarised perpendicular to the field;
these will have energy shifts of ± 32 µB B and ±2µB B.

6. (i) First two terms represent interaction between the magnetic moments of
electron and proton respectively with the external field B; the final term
represents the spin-spin (hyperfine) interaction between the electron and
proton.
(ii) Neglecting the term in µp , and making use of the identity σ (e) · σ (p) =
(e) (p) (e) (p) (e) (p)
σz σz + 12 (σ+ σ− + σ+ σ− ), where
# $ # $ # $
0 1 0 2 0 0
σz = , σ+ = , σ− = .
1 0 0 0 2 0

We therefore have

σ (e) · σ (p) | ↑e " ⊗ | ↑p " = | ↑e " ⊗ | ↑p "

σ (e) · σ (p) | ↑e " ⊗ | ↓p " = −| ↑e " ⊗ | ↓p " + 2| ↓e " ⊗ | ↑p " ,

etc. From these results, we can deduce the matrix elements of the Hamil-
tonian and confirm the expression given in the problem.

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16.3. PROBLEM SET III 214

(iii) By inspection, the states | ↑e " ⊗ | ↑p " and | ↓e " ⊗ | ↓p " are energy eigen-
states with energies W + b and W − b respectively. The other two energy
eigenvalues are given by the solutions of
% %
% b−W −E 2W %
% % = 0,
% 2W −b − W − E %
√
which leads to E = −W ± 4W 2 + b2 . In the case where b . W , i.e.
where the external magnetic field is very weak, these reduce to W +b2 /2W
and −3W − b2 /2W , so there is a triplet of S = 1 states with energy close
to W , and the singlet S = 0 state with energy close to −3W . In the other
limit where b / W , i.e. where the external magnetic field is very strong,
this expression reduces to ±b, so we have two states with energy close to
+b and two close to −b, corresponding to the two possible orientations of
the electron spin.

7. Taking the 1s hydrogen wavefunctions as our basis, the matrix elements of the
Hamiltonian are defined in the question. Neglecting the overlap integrals, the
upper bound E on the energy levels is given, according to the Rayleigh-Ritz
variational method, by setting the determinant of the matrix Hij − Eδij to
zero. Multiplying out, and factorizing, this condition translates to the relation
* +
(α − E − γβ) (α − E)2 + γβ(α − E) − 2β 2 = 0 .

This has three solutions:

1 , - .
E = α − γβ, α + β γ ± γ2 + 8 .
2
As θ → 60◦ we expect γ → 1, as all the bond lengths become equal. The
solutions in this limit are: E = α − β, α − β, and α + 2β. As θ → 180◦ we
expect γ → 0, as atoms√1 and 3 become separated. The solutions in this limit
are: E = α, and α ± 2β. Noting that β < 0, the lowest energy is α + 2β
corresponding to θ = 60◦ , so the stable configuration should be an equilateral
triangle. Since this state is non-degenerate, it can only accommodate the two
electrons of the H+ 3 ion if they are in an antisymmetric singlet (S = 0) spin
state.

8. Defining (with obvious notation) |VB" = C[|a1 " ⊗ |b2 " + |b1 " ⊗ |a2 "], we have:

(i) the normalization |VB": !VB|VB" = C 2 [!a1 |a1 "!b2 |b2 " + 2!a1 |b1 "!b2 |a2 " + !b1 |b1 "!a2 |a2 "] =
C 2 (2 + 2SS ∗ ), and hence C 2 = 12 (1 + SS ∗ ).
(ii) Defining
- the normalized bonding and-antibonding orbitals, |g" = (|a" +
|b")/ 2(1 + S) and |u" = (|a" − |b")/ 2(1 − S), we have
/ / / /
1+S 1−S 1+S 1−S
|a" = |g" + |u", |b" = |g" − |u" .
2 2 2 2
As a result, we find that |VB" = C[(1 + S)|g1 " ⊗ |g2 " − (1 − S)|u1 " ⊗ |u2 "].
(iii) The state orthogonal to |VB" is then given by |ψ⊥ " = C[(1 − S)|g1 " ⊗
|g2 " + (1 + S)|u1 " ⊗ |u2 "]. Rewriting this in the |a" and |b" basis, after a
little algebra we arrive at:

C(1 + S 2 ) 2CS
|ψ⊥ " = {|a1 " ⊗ |a2 " + |b1 " ⊗ |b2 "} − {|a1 " ⊗ |b2 " + |b1 " ⊗ |a2 "} ,
(1 − S )
2 (1 − S 2 )
of which the first term represents the ionic component and the second the
covalent, i.e.

(1 + S 2 ) 2S
|ψ⊥ " = |IB" − |VB" .
(1 − S 2 ) (1 − S 2 )

Advanced Quantum Physics

16.3. PROBLEM SET III 215

(iv) Inserting the given value of ρ gives S = 0.697, and hence the ratio of
2
IB/VB in the state |ψ⊥ ": IB/VB = [ (1−S ) 2
2S ] = 0.14.

9. For the rotation/vibration system, the energy levels have the form

!2 J(J + 1)
E = E0 + (n + 1/2)!ω + ,
2I
and the selection rules are ∆n = ±1 and ∆J = ±1. Thus, neglecting any
change in the moment of inertia, we have the following energy changes:

!2
R branch J → J + 1 J = 0, 1, 2 · · · ∆E = !ω + (J + 1)
I
!2
P branch J → J − 1 J = 1, 2 · · · ∆E = !ω − J
I
(i) The above formulae imply equally spaced lines above and below !ω, but
the transition at !ω (∆J = 0, the Q-branch) is not permitted by the
parity change selection rule.
(ii) The double peaks are an isotope effect. Cl has two isotopes 35 Cl and
37
Cl with abundances in the ratio of roughly 3:1. The less abundant 37 Cl
will have a larger reduced mass (by about 1 part in 1000) and thus a
lower vibration frequency. Thus there are two separate spectra slightly
displaced in frequency.
(iii) The uneven spacing results from the change in moment of inertia. If
!2 /2I ≡ B initially and B + δB finally (with δB < 0), the formulae for
the energy changes become:

R − branch J → J + 1 ∆E = !ω + 2B(J + 1) + δB(J + 1)(J + 2)

P − branch J → J − 1 ∆E = !ω − 2BJ + δBJ(J − 1)

So the spacing in the R-branch above !ω decreases with increasing J while

that in the P-branch increases with J.
(iv) The intensity of absorption depends on the population of the states, which
is given by the product of the degeneracy of the rotational wavefunction
and the Boltzmann factor, i.e. (2J + 1) exp (−J(J + 1)!2 /2IkB T ), which
exhibits first a rise and then a fall with increasing J, as observed.

From the central vibrational frequency ω we can-infer the force constant of the
bond k: ω = 2πν 1 5.4 × 1014 Hz. Then, ω = k/µ, where µ is the reduced
mass (approximately equal the mass of the Hydrogen atom in this case), so we
deduce that k = 490 Nm−1 .

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16.4. PROBLEM SET IV 216

16.4 Problem Set IV

1. Operator methods in quantum mechanics: The following problem
combines the practice of a number different methodologies covered in this
course. Here we address the excitation spectrum of a quantum mechani-
cal spin chain. It provides a counterpart to the vibrational modes of the
quantum harmonic chain considered in lectures. Here we will address the
problem in two different ways.
In strongly correlated solid state systems, the Coulomb interaction can
result in electrons becoming localized to the sites of the underlying crys-
talline lattice – the Mott transition. However, in these insulating ma-
terials, the spin degrees of freedom carried by the constituent electrons
can remain mobile – spin fluctuations can be exchanged between neigh-
bouring electrons without motion! of charge. Such systems are described
by quantum magnets, Ĥ = m!=n Jmn Ŝm · Ŝn , where exchange cou-
plings Jmn denotes the matrix elements coupling lattice sites m and n.
Since these matrix elements decay rapidly with distance, it is often legit-
imate to restrict attention to neighbouring sites. Although these matrix
elements are typically positive (leading to an antiferromagnetic cou-
pling), in the following we will consider them negative leading to ferro-
magnetism – i.e. neighbouring spins want to lie parallel. Consider then
the one-dimensional spin S quantum (Heisenberg) ferromagnet,
"
Ĥ = −J Ŝm · Ŝm+1 ,
m

α , Ŝ β ] =
where J > 0, and the spins obey the quantum spin algebra , [Ŝm n
γ
i!δmn "αβγ Ŝm .

(a) Making use of the spin commutation relations and Ehrenfest’s the-
orem, show that, in the Heisenberg representation, the spins obey
the equations of motion,

dŜm
! = J Ŝm × (Ŝm+1 + Ŝm−1 ) ,
dt
where we suppose that the boundary conditions are periodic, i.e.
Sm+N = Sm .
(b) For large spin S, we may take the spin expectation values to be
defined by their classical values, #Ŝm $ = Sm . Moreover, if we are
interested in low-energy excitations of the spin chain, only modes
of long wavelength contribute (cf. the vibrational modes of the
harmonic chain). In this case, we may develop the Taylor series ex-
pansion, Sm+1 = Sm +∂Sm + 12 ∂ 2 Sm +· · ·, where the lattice spacing
is taken as unity. In doing so, show that the leading contribution
to the equations of motion in the gradient expansion is given by,

Ṡ = JS × ∂ 2 S .

(c) Show that the solution

√ to this equation is given by S(x, t) = (c cos(kx−
ωt), c sin(kx−ωt), S 2 − c2 ) and determine the dispersion relation,
ω(k). Sketch a “snapshot” configuration of the spins in the chain.
These low energy modes of the quantum spin chain are known as a
spin waves and mirror the phonon excitations of the quantum harmonic

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16.4. PROBLEM SET IV 217

chain. Notice that the dispersion relation in this case has a quadratic
dependence on k (cf. non-relativitic particles) as opposed to the lin-
ear dependence of the phonon spectrum. If you are feeling energetic,
you might contemplate the spin wave modes for the antiferromag-
netic chain where the dispersion becomes linear. Let us now consider
an alternative approach to the spin wave spectrum which follows an
operator-based formalism.
(d) Defining the spin raising and lowering operators, Ŝ ± = Ŝ x ± iŜ y ,
show that the ferromagnetic Heisenberg model can be written as
"# 1$ + − %&
− +
Ĥ = −J Ŝm+1 +
z z
Ŝm Ŝm Ŝm+1 + Ŝm Ŝm+1 .
m
2

Then, making use of the Holstein–Primakoff spin representation In lectures, we have discussed the
√ †
− = ! 2S a† (1 − am am )1/2 , Ŝ + = (Ŝ − )† , Fourier series expansion,
(defined on page 192), Ŝm m 2S m m
z = !(S −a† a ) where [a , a† ] = δ
and Ŝm m m m n mn , show that the Hamil- 1 "
f (x) = √ fk eikx
tonian can be expanded as a bilinear (i.e. to quadratic order) in L k
the raising and lowering operators, ' L
1
" † fk = √ f (x)e−ikx
Ĥ = −JN S 2 + S (am+1 − a†m )(am+1 − am ) + O(S 0 ) . L 0
m
In the following, we are deal-
(e) Being bilinear in operators (i.e. quadratic), the Hamiltonian can ing with a discrete lattice where
be diagonalized by discrete Fourier transformation. With periodic we have to consider the discrete
Fourier representation,
boundary conditions, a†m+N = a†m , defining
1 "
N
" fn = √ fk eikn
1 1 " −ikm † N k
a†k = √ eikm a†m , a†m =√ e ak ,
N m=1
N k 1 "
fk = √ fn e−ikn .
N n
where the sum on k = 2πn/N , runs over the N integers n =
−N/2 + 1, −N/2 + 2 · · · N/2, show that the transformed operators
obey the commutation relations, [ak , a†k! ] = δkk! . In the Fourier
representation, show that
"
Ĥ = −JN S 2 + !ωk a†k ak + O(S 0 )
k

where ωk = 2JS(1 − cos k) = 4JS sin2 (k/2) represents the disper-

sion of the spin excitations.
In the long wavelength limit, k → 0, the energy of the excitations
vanishes, ωk → JSk 2 . These low-energy excitations, known as spin
waves or magnons, describe the elementary spin-wave excitations
of the ferromagnet. Taking into account terms at higher order in the
parameter 1/S, one finds interactions between the magnons.
Measurements of the spin-wave
dispersion relations for the ferro-
magnet La0.7 Sr0.3 MnO3 .
2. The following problem involves some revision of time-dependent perturba-
tion theory and then applies the methodology to the problem of an induced
transition in a hydrogen atom.
Suppose that a system is prepared in an energy eigenstate ψ0 at time t =
0 when a weak perturbation V (t) is applied. Show that the probability
of finding the system in state ψn at time t is given approximately by
|cn (t)|2 where
'
1 t # i(En −E0 )t! /!
cn (t) = dt e #ψn |V (t# )|ψ0 $ .
i! 0

Advanced Quantum Physics

16.4. PROBLEM SET IV 218

At times t > 0, an electric field Ez = E0 exp −t/τ is applied to a hydrogen

atom, initially prepared in its ground state. Working to first order in
the electric field, find the probability that, after a long time, t ' τ , the
atom is in (i) the 2s state, and (ii) one of the 2p states (state which
one?).

3. This problem addresses the question of spontaneous emission in hydrogen.

Use the formula for the Einstein A-coefficient derived in class to calculate You will need the same matrix
the lifetime of the 2p state of atomic Hydrogen. elements as you computed in the
previous problem.
Without detailed evaluation of the matrix element, explain why the 3s
level of hydrogen has a lifetime roughly 100 times longer than the 2p
level. And why is the lifetime of the 2s level very much longer than 2p,
by a factor ∼ 108 ?

4. Scattering theory: The following problem revises the derivation of the Born
approximation and then applies it to the high energy scattering from an
attractive square well potential.
Show that the Born approximation yields the following expression for
the elastic scattering of a particle of mass m and momentum !k from a
spherically symmetric potential V (r),
( ) *' *2
dσ 2m 2 ** ∞ *
* ,
= * V (r)r sin (Kr)dr *
dΩ !2 K 0

where K = 2k sin(θ/2) and θ is the angle through which the particle is

scattered.
Obtain the differential cross-section for scattering from a potential,
#
−V0 r ≤ a
V (r) =
0 r>a
and verify that the scattering is isotropic when the energy of the incident
particle or the size of the scatterer is sufficiently low, so that Ka * 1.
Obtain an expression for the total cross-section in this limit.

5. Scattering theory: The following problem involves the application of the

partial wave scattering method to a simplified model of a nucleus.
As a crude model for an effective nuclear potential which binds together
protons and neutrons, consider a repulsive radial shell potential, V (r) =
!2
2m U0 δ(r − R).

(a) Calculate the s-wave scattering phase shift as a function of U0 .

(b) Assuming that U0 ' 1/R and U0 ' k, show that if tan(kR) is not
close to zero, the phase shift resembles that of a hard sphere.
(c) Continuing with these assumptions show that, if tan(kR) is close
(but not equal to) zero, resonance is possible (i.e. the cross sec-
tion reaches its maximum value). Compare the resonance energy
with that of a bound state of the spherical shell with an infinitely
impenetrable wall. This is an example of a “scattering resonance”,
when the incident energy matches a quasi bound-state.

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16.4. PROBLEM SET IV 219

6. † Relativistic quantum mechanics: The following problem establishes an im-

portant relation in the study of relativistic covariance in lectures.
In lectures, it was shown that Lorentz covariance of the Dirac equation
relies on the condition S(Λ)γ µ S −1 (Λ) = (Λ−1 )µν γ ν . For an infinitesimal
proper Lorentz transformation Λµν = g µν +ω µν , S(Λ) = I− 4i Σµν ω µν +· · ·,
where ωµν and Σµν are antisymmetric. Show that, to leading order in
ω, this condition translates to
$ %
[γ µ , Σαβ ] = 2i g µα γβ − g µβ γα .

Show that the following represents a consistent solution, Σαβ = 2i [γα , γβ ].

7. Relativistic quantum mechanics: In lectures, we used the relativistic covari-

ance of the Dirac equation to deduce the existence of an intrinsic angular
momentum known as spin. In the following problem, we can establish the
consistency of this construction by showning that the Dirac Hamiltonian
commutes with the total angular momentum, Ĵ.
Verify that the Dirac Hamiltonian Ĥ = α · p̂ + βm commutes with both
the helicity operator S · p/|p|, and the angular momentum Ĵ = L̂ + S
where L̂ = x × p̂.

8. † Relativistic quantum mechanics: The following problem relates to the vac-

uum instability and the stimulation of particle/antiparticle pairs.
Following on from the discussion of the potential step in lectures, con-
sider the problem of the transmission through a potential barrier of width
a and hight eV . Applyly the boundary conditions at the edge of the bar-
rier, show that the transmission probability is given by
* *
2 *−2
# (1 + ζ ) *
*
* #
|t | = *cos(p a) − i sin(p a)
2
,
2ζ *
p! (p0 +m) #
where ζ = p(p0 ! +m)
, E ≡ p0 , and E # ≡ p0 = E − eV . Analyse the
#
transmission probability in the energy ranges p0 ≡ E # > m, −m < E # <
m, and E # < −m. In the third regime, explain why a condition of perfect
transmission can be obtained.

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16.4. PROBLEM SET IV 220

Answers: Problem set IV

1. (a) From Ehrenfest’s theorem, the equation of motion for the spin is given
by −i! dŜdtm = [Ĥ, Ŝm ]. Making use of the spin commutation relation, we
have (summation on repeated spin indicies assumed)
β
dŜm
−i! = −J[Ŝm
α β
, Ŝm ](Ŝm+1
α
+ Ŝm−1
α
) = −i!J!αβγ Ŝm
γ
(Ŝm+1
α
+ Ŝm−1
α
).
dt
We thus obtain the required equation of motion.
(b) Since Sm+1 +Sm−1 " 2S|x=m +∂ 2 S|x=m and, for classical vectors, S×S =
0, we obtain the required equation of motion.
(c) Substituting the √
expression for S(x, t), we find that the equation is solved
with ω(k) = Jk 2 S 2 − c2 . The corresponding spin configuration is shown
right.
(d) Substituting for the spin raising and lowering operators, the identity is
clear. Expanding to the spin raising and lowering operators to leading
†
order in a2Sa about the ferromagnetic ground state (in which all spins are
aligned along êz , we obtain
!" # $%
Ĥ = −JN S 2 + JS a†m am + a†m+1 am+1 − a†m am+1 + h.c. + O(S 0 ) ,
m

where h.c. denotes the Hermitian conjugate. Rearranging, we obtain the

required expression for the Hamiltonian.
(e) With the definitions given in the problem,
1 ! −ikm+ik! n 1 ! −i(k−k! )m
[ak , a†k! ] = e [am , a†n ] = e = δkk! .
N m,n & '( ) N m
δmn

Then subtituted into the Hamiltonian,

! 1 ! ! !
Ĥ = −JN S 2 + S ei(k−k )m (eik − 1)(e−ik − 1)a†k ak!
N m
kk!
& '( )
δkk!
!
= −JN S + S
2
|e − 1|2 a†k ak .
ik

From this result we obtain the required dispersion relation.

2. Standard bookwork allows a derivation of the amplitude cn (t). In the present

case, with V (t) = eE0 ze−t/τ , the matrix element %ψ2s |z|ψ1s & = 0 since the 1s
and 2s wavefunctions both have even parity while z has odd parity. Therefore
the probability of finding the atom in the 2s state is identically zero.
The matrix elements %ψ2p±1 |z|ψ1s & = 0 since the φ part of the integral will
vanishes,
* 2π
%ψ2p±1 |z|ψ1s & ∼ dφe±iφ = 0 .
0

The only non-zero matrix element is:

+ ,1/2 + ,1/2 * *
1 1
%ψ2p0 |z|ψ1s & = 2 2 −r/a0 −r/2a0
r dr r e e 2π sin θdθ cos2 θ
32πa50 πa30
1 4! 4π 256a0
= √ · · = √ .
4 2πa40 (3/2a0 )5 3 243 2
Taking the limit as t → ∞, the t" integral is given by,
* ∞
! ! 1
dt" e−t /τ ei(E2p −E1s )t /! = ,
0 1/τ − i∆E/!

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16.4. PROBLEM SET IV 221

where ∆E = E2p − E1s = 3R∞ /4. Putting all this together we obtain the
probability of being in the 2p0 state after a long time as
e2 E02 a20 215 1
|c2p0 (∞)|2 = · .
3 10 ∆E + !2 /τ 2
2

3. From the lecture notes, the decay rate for unpolarized light is given by,
ω 3 |dkj |2
A= ,
3π!0 c3 !
and the lifetime is thus τ = 1/A. Take for example the 2p0 state of Hydrogen
decaying to 1s (the other 2p states must have the same lifetime, but this one
depends on the same matrix elements that we computed in in the previous
question. Only the z-component of d is non-zero for this transition, (the φ
integral yields zero if you compute the matrix elements of x or y) giving,
256ea0
%2p0 | ez |1s& = √ = 6.31 × 10−30 Cm .
243 2
The energy of the emitted photon is
3 3 me4
!ω = R∞ = · ⇒ ω = 1.56 × 1016 Hz .
4 4 2(4π!0 )2 !2
Hence, the lifetime of the state is τ = 1.56 × 10−9 s.
The only lower lying state to which 3s can decay is 2p according to the selection
rules. We can expect the matrix element %3s| ez |2p& ∼ ea0 on dimensional
grounds, and thus not very different from %2p| ez |1s&. The main difference
between the lifetimes of the 3s and 2p levels will arise from the difference in
ω 3 . For the 3s→2p transition,
1 1 5
!ω = ( − )R∞ = R∞ .
4 9 36
The ratio of the lifetimes is therefore approximately
+ ,3
τ (3s) 3 36
∼ · ∼ 150 .
τ (2p) 4 5
The only state lying below 2s is 1s, but the decay 2s→1s is not allowed by
the electric dipole selection rules. The 2s state is “metastable”. The dominant
decay is actually via two-photon emission, a process which can arise through
second order perturbation theory, and occurs very slowly. In practice, atoms
may well make transitions from 2s to 2p (for example) before decay takes place
as a result of collision processes. Alternatively, decay of the 2s state may be
induced by the application of an external electric field, which mixes 2s and 2p
through the Stark effect.

4. From the lecture notes, the Born Approximation gives,

dσ - m .2 //* /2
/
= / V (r)ei∆·r d3 r/ ,
dΩ 2π! 2 / /

where ∆ is the difference beweeen incoming and outgoing wave vectors, of

magnitude 2k sin2 (θ/2). In the case where V (r) = V (r), i.e. where the potential
is centrally symmetric, it is convenient to take ∆ as the axis of polar coordinates
for the purpose of integration, so that ∆ · r = |∆|r cos θ" . The integral thus
becomes
* *
i∆·r 3 !
V (r)e d r = V (r)ei∆r cos θ 2π sin θ" dθ" r2 dr
* 0 !
1π *
ei∆r cos θ 4π
= 2π V (r)r dr 2
= V (r)rdr sin(∆r) ,
i∆r ∆
0

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16.4. PROBLEM SET IV 222

and hence
+ ,2 / * /2
dσ 2m / /
/ V (r)rdr sin(∆r)/ .
= / /
dΩ ∆!2

Taking V (r) = −V0 for r ≤ a, and V (r) = 0 otherwise, the integral becomes
(integrating by parts),
* a 23 4a * a 5
cos(∆r) cos(∆r)
−V0 r sin(∆r)dr = −V0 −r + dr
0 ∆ 0 0 ∆
V0
= − 2 (sin(∆a) − ∆a cos(∆a)) ,
∆
and thus
3 42
dσ 2mV0
= (sin(∆a) − ∆a cos(∆a)) .
dΩ !2 ∆ 3
In the low energy limit, ∆ → 0,
1
sin(∆a) − ∆a cos(∆a) ≈ ∆a − (∆a)3 − ∆a(1 − (∆a)2 /2) = (∆a)3 /3 ,
3!
and hence
+ ,2
dσ 2mV0 a3
= .
dΩ 3!2
This is independent of ∆ and hence independent of θ, so isotropic, as required.
The total cross-section is obtained by integrating over solid angles, which simply
involves multiplying by 4π in this case
+ ,2
2mV0 a3
σtot = 4π .
3!2

5. (a) When kR - 1, s-wave scattering dominates. In this case, the problem is

equivalent to a one-dimensional scattering problem with an infinite wall
at the origin and a δ-function repulsive potential at r = R.
The wavefunction has the solution,
2
C sin kr r<R
u(r) =
sin(kr + δ0 ) r > R

From the continuity condition on the wavefunction and the derivative, we

obtain

A sin(kR) = sin(KR + δ0 )
kA cos(kR) − k cos(kR + δ0 ) = U0 sin(kR + δ0 ) .

From the first equation, we obtain A = sin(kR+δ

sin(kR)
0)
which substituted into
the second equation, leads to the relation
3 4
k tan(kR)
δ0 = tan−1 − kR .
k − U0 tan(kR)
The structure is similar to that obtained for the spherical square potential
but with different resonant behaviour.
(b) With U0 . 1/R, k, and U0 tan(kR) . k, we obtain the resonance condi-
tion
k tan(kR) k
" " 0,
k − U0 tan(kR) −U0 tan(kR)
i.e. δ0 " −kR, the value that it would have for a hard sphere.

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16.4. PROBLEM SET IV 223

(c) Now supose that tan(kR) is small. In this case, we have a resonance when
k − U0 tan(kR) = 0, i.e. tan(kR) = Uk0 - 1, and
π π
δ0 = − kR " .
2 2
The cross-section σ0 = 4π
k2 sin δ0 " k2 . The resonance is near tan(kR) =
2 4π

0, which implies that kR = (2n+1)π/2, the quasi-bound state of the well.

6. Substituting the definition of S(Λ) into the defining condition we obtain

+ , + ,
i i i
1 − Σαβ ω αβ γ µ 1 + Σγδ ω γδ = γ µ + [γ µ , Σαβ ] ω αβ + · · ·
4 4 4
= (g µν − ω µν ) γ ν .

Rearranging the left and right hand sides, we obtain

i µ
[γ , Σαβ ] ω αβ = −ω βα g µβ γα ≡ ω αβ g µβ γα ,
4
from which we obtain the required identity. The latter equation is shown to be
consistent with the solution Σαβ = (i/2)[γα , γβ ] by making use of the anticom-
mutation relation of the γ matrices.

7. Using the identity

+ , + ,
0 [σi , σj ] 0 σk
[α · p̂, S · p̂] = p̂i p̂j = 2i!ijk p̂i p̂j .
[σi , σj ] 0 σk 0
Therefore, since p̂ × p̂ = 0, we find that the Hamiltonian commutes with the
Helicity operator.
Turning to the angular momentum, taking each term separately,

[Ĥ, L̂i ] = !ijk [α · p̂, x̂j p̂k ] = !ijk (αl p̂l x̂j p̂k − x̂j p̂k αl p̂l )
= !ijk (−iαl δlj p̂k ) = −iα × p̂ .
1
[Ĥ, S] = [α · p̂, S] = (αi p̂i σj − σj αi p̂i )
3+ 2 , + ,4 + ,
1 0 σ · p̂ σ 0 1 0 1
= , = [σ · p̂, σ]
2 σ · p̂ 0 0 σ 2 1 0
+ ,
0 1
= −i p̂ × σ = −ip̂ × α.
1 0

Putting these terms together we find [Ĥ, Ĵ] = 0.

8. Applying the plane wave solution of the Dirac equation ψ(p) = e−p·x u(p) (de-
fined in this form for positive and negative energy states) to the two edges of
the potential step, we obtain the boundary conditions
   
1 1
 0  −ipa/2  0  ipa/2
 p e +r  p e
E+m − E+m
0 0
   
1 1
 0  !  0 !  ip! a/2
= t"  p!  e−ip a/2 + r"  e
E ! +m − E !p+m
0 0
     
1 1 1
 0  !  0 !  −ip a/2
!  0 
t"  p!  eip a/2 + r"  e = t  p  eipa/2 ,
E ! +m − E !p+m E+m
0 0 0

Advanced Quantum Physics

16.4. PROBLEM SET IV 224

where the reflection and transmission coefficients are defined in the figure.
From these equations we obtain
! !
2e−ipa/2 = t" (1 + ζ)e−ip a/2 + r" (1 − ζ)eip a/2
! !
2reipa/2 = t" (1 − ζ)e−ip a/2 + r" (1 + ζ)eip a/2
! !
teipa/2 = eip a/2 t" + e−ip a/2 r"
- ! !
.
teipa/2 = ζ eip a/2 t" − e−ip a/2 r" .

Rearranging these equations we obtain

2 1 −i(p−p! )a/2
r" = !a e ,
1 + ζ µe−ip !a −1
−µ e −ip

where µ = (1 − ζ)/(1 + ζ). Finally, with this result, we obtain

1
t = e−ipa
cos(p" a) − i sin(p" a)(1 + ζ 2 )/2ζ

From this result, we obtain the expression for the transmitted current shown
in the question.
For energies E " > m, the particles traverse the barrier as a plane wave. In
particular, when p" a = nπ there is perfect transmission. For m > E " > −m,
p" is imaginary and exchange of particles occurs by resonant tunnelling across
the barrier. For energies E " < −m, the Klein paradox regime, p" is real and
positive, and there is again perfect transmission when p" a = nπ. Here the
transmission is mediated by negative energy states under the barrier.

Advanced Quantum Physics