Chapter 1

Wave mechanics and the

Schrodinger equation
Although this lecture course will assume a familiarity with the basic concepts
of wave mechanics, to introduce more advanced topics in quantum theory, it
makes sense to begin with a concise review of the foundations of the subject.
In particular, in the rst chapter of the course, we will begin with a brief
discussion of the historical challenges that led to the development of quantum
theory almost a century ago.
William Thomson, 1st Baron
Kelvin 1824-1907
Kelvin was ed-
ucated at Glas-
gow and Cam-
bridge. He be-
came professor of
natural philoso-
phy at Glasgow in
1846. From 1846
to 1851 Kelvin
edited the Cambridge and Dublin
Mathematical Journal, to which he
contributed several important papers.
Some of his chief discoveries are an-
nounced in the Secular Coating of
the Earth, and the Bakerian lec-
ture, the Electrodynamic Qualities
of Metals. He invented the quad-
rant, portable, and absolute elec-
trometers, and other scientic instru-
ments. In January 1892, he was
raised to the peerage as Lord Kelvin.
The formulation of a consistent theory of statistical mechanics, electrody-
namics and special relativity during the latter half of the 19th century and
the early part of the 20th century had been a triumph of unication. How-
ever, the undoubted success of these theories gave an impression that physics
was a mature, complete, and predictive science. Nowehere was condence
expressed more clearly than in the famous quote made at the time by Lord
Kelvin: There is nothing new to be discovered in physics now. All that re-
mains is more and more precise measurement. However, there were a number
of seemingly unrelated and unsettling problems that challenged the prevailing
theories.
1.1 Historical foundations of quantum physics
1.1.1 Black-body radiation
Gustav Robert Kirchho 1824-
1887
A German
physicist who
contributed to
the fundamental
understanding of
electrical circuits,
spectroscopy,
and the emission
of black-body
radiation by heated objects. He
coined the term black body
radiation in 1862, and two sets of
independent concepts in both circuit
theory and thermal emission are
named Kirchhos laws after him.
In 1860, Gustav Kirchho introduced the concept of a black body, an ob-
ject that absorbs all electromagnetic radiation that falls upon it none passes
through and none is reected. Since no light is reected or transmitted, the
object appears black when it is cold. However, above absolute zero, a black
body emits thermal radiation with a spectrum that depends on temperature.
To determine the spectrum of radiated energy, it is helpful to think of a black
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,
the number of modes, per unit frequency per unit volume is given by
N()d =
8
2
c
3
d ,
where, as usual, c is the speed of light.
1
John William Strutt, 3rd Baron
Rayleigh OM (1842-1919)
An English physi-
cist who, with
William Ramsay,
discovered the el-
ement argon, an
achievement for
which he earned
the Nobel Prize
in 1904. He also
discovered the
phenomenon of Rayleigh scattering,
explaining why the sky is blue, and
predicted the existence of surface
waves known as Rayleigh waves.
1
If we take the cavity to have dimension L
3
, the modes of the cavity involve wave numbers
k = n/L where n = (nx, ny, nz) denote the vector of integers nx = 0, 1, 2, , etc. The
corresponding frequency of each mode is given by = c|k|/2, where c is the velocity of
light. The number of modes (per unit volume) having frequencies between and + d is
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
2
dependence.
The amount of radiation emitted in a given frequency range should be
proportional to the number of modes in that range. Within the framework
Max Karl Ernst Ludwig Planck
1858-1947
German physicist
whose work
provided the
bridge between
classical and
modern physics.
Around 1900
Planck developed
a theory explain
the nature of
black-body radiation. He proposed
that energy is emitted and absorbed
in discrete packets or quanta,
and that these had a denite size
Plancks constant. Plancks nding
didnt get much attention until the
idea was furthered by Albert Einstein
in 1905 and Niels Bohr in 1913.
Planck won the Nobel Prize in 1918,
and, together with Einsteins theory
of relativity, his quantum theory
changed the eld of physics.
of classical statistical mechanics, each of these modes have an equal chance
of being excited, and the average energy in each mode is k
B
T (equipartition),
where k
B
is the Boltzmann constant. The corresponding energy density is
therefore given by the Rayleigh-Jeans law,
(, T) =
8
2
c
3
k
B
T .
This result predicts that (, T) increases without bound at high frequencies,
the untraviolet (UV) catastrophe. However, such behaviour stood in
contradiction with experiment which revealed that the short-wavelength de-
pendence was quite benign (see, e.g., Fig. 1.1).
To resolve diculties presented by the UV catastrophe, Planck hypothe-
sized that, for each mode , energy is quantized in units of h, where h denotes
the Planck constant. In this case, the energy of each mode is given by
2
() =

n=0
nhe
nh/k
B
T

n=0
e
nh/k
B
T
=
h
e
h/k
B
T
1
,
leading to the anticipated suppression of high frequency modes. From this
result one obtains the celebrated Planck radiation formula,
(, T) =
8
2
c
3
() =
8h
3
c
3
1
e
h/k
B
T
1
. (1.1)
This result conforms with experiment (Fig. 1.1), and converges on the Rayleigh-
Jeans law at low frequencies, h/k
B
T 0.
Albert Einstein 1879-1955
was a German-
born theoretical
physicist. He is
best known for
his theory of rela-
tivity and speci-
cally mass-energy
equivalence, ex-
pressed by the
equation E =
mc
2
. Einstein received the 1921 No-
bel Prize in Physics for his services
to Theoretical Physics, and especially
for his discovery of the law of the pho-
toelectric eect.
Plancks result suggests that electromagnetic energy is quantized: light of
wavelength = c/ is made up of quanta each of which has energy h. The
equipartion law fails for oscillation modes with high frequencies, h k
B
T. A
therefore given by N()d =
1
L
3
2
1
8

(4k
2
)dk
(/L)
3
, where the factor of 2 accounts for the two
polarizations, the factor (4k
2
)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 (/L)
3
denotes the volume of phase space occupied by
each mode. Rearranging the equation, and noting that dk = 2d/c, we obtain the relation
in the text.
2
If we dene the partition function, Z =
P

n=0
e
nh
, where = 1/kBT, E =

lnZ. Making use of the formula for the sum of a geometric progression,
P

n=0
r
n
=
1/(1 r), we obtain the relation.
Advanced Quantum Physics
1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 3
Figure 1.2: Measurements of
the photoelectric eect 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-
likans Nobel Lecture, The Elec-
tron and the Light-Quanta from
the Experimental Point of View,
The Nobel Foundation, 1923.
quantum theory for the specic heat of matter, which takes into account the
quantization of lattice vibrational modes, was subsequently given by Debye
and Einstein.
1.1.2 Photoelectric eect
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 gure, 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 Maxwells 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 Plancks
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-
old energy, the work function W of the metal, has the required energy to
eject a single electron, creating the observed eect. In particular, Einsteins
theory was able to predict that the maximum kinetic energy of electrons emit-
ted by the radiation should vary as
k.e.
max
= h W .
Robert Andrews Millikan 1868-
1953
He received
his doctorate
from Columbia
University and
taught physics
at the University
of Chicago
(1896-1921)
and the Cali-
fornia Institute
of Technology (from 1921). To
measure electric charge, he devised
the Millikan oil-drop experiment. He
veried Albert Einsteins photoelec-
tric equation and obtained a precise
value for the Planck constant. He
was awarded the 1923 Nobel Prize in
physics.
Later, in 1916, Millikan was able to measure the maximum kinetic energy of
the emitted electrons using an evacuated glass chamber. The kinetic energy of
the photoelectrons were found by measuring the potential energy of the electric
eld, eV , needed to stop them. As well as conrming the linear dependence of
the kinetic energy on frequency (see Fig. 1.2), by making use of his estimate
for the electron charge, e, established from his oil drop experiment in 1913, he
was able to determine Plancks constant to a precision of around 0.5%. This
discovery led to the quantum revolution in physics and earned Einstein the
Nobel Prize in 1921.
1.1.3 Compton Scattering
Arthur Holly Compton 1892-
1962:
An American
physicist, he
shared the 1927
Nobel Prize in
Physics with C.
T. R. Wilson for
his discovery of
the Compton ef-
fect. In addition
to his work on
X rays he made valuable studies of
cosmic rays and contributed to the
development of the atomic bomb.
In 1923, Compton investigated the scattering of high energy X-rays and -ray
from electrons in a carbon target. By measuring the spectrum of radiation at
dierent angles relative to the incident beam, he found two scattering peaks.
The rst peak occurred at a wavelength which matched that of the incident
beam, while the second varied with angle. Within the framework of a purely
classical theory of the scattering of electromagnetic radiation from a charged
Advanced Quantum Physics
1.1. HISTORICAL FOUNDATIONS OF QUANTUM PHYSICS 4
particle Thomson scattering the wavelength of a low-intensity beam should
remain unchanged.
3
Comptons observation demonstrated that light cannot be explained purely
as a classical wave phenomenon. Light must behave as if it consists of particles
Figure 1.3: Variation of the
wavelength of X rays scattered
from a Carbon target. A. H.
Compton, Phys. Rev. 21, 483;
22, 409 (1923)
in order to explain the low-intensity Compton scattering. If one assumes that
the radiation is comprised of photons that have a well dened momentum as
well as energy, p =
h
c
=
h

, the shift in wavelength can be understood: The

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 dierent 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 can be derived,
4
=

=
h
m
e
c
(1 cos ) .
The constant of proportionality h/m
e
c = 0.002426 nm, the Compton wave-
length, characterizes the scale of scattering. Moreover, as h 0, one nds
that 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 diuse 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
energy leading to the eventual collapse of the electron into the nucleus. More-
over, as the electron spirals inwards, the emission would gradually increase
in frequency leading to a broad continuous spectra. Yet, detailed studies of
electrical discharges in low-pressure gases revealed that atoms emit light at
discrete frequencies.
Ernest Rutherford, 1st Baron
Rutherford of Nelson, 1871-
1937
was a New
Zealand born
British chemist
and Physicist
who became
known as the
father of nuclear
physics. He
discovered that
atoms have a
small charged nucleus, and thereby
pioneered the Rutherford model
(or planetary model of the atom,
through his discovery of Rutherford
scattering. He was awarded the
Nobel Prize in Chemistry in 1908.
He is widely credited as splitting the
atom in 1917 and leading the rst
experiment to split the nucleus in
a controlled manner by two students
under his direction, John Cockcroft
and Ernest Walton in 1932.
The clue to resolving these puzzling observations lay in the discrete nature
of atomic spectra. For the hydrogen atom, light emitted when the atom is
thermally excited has a particular pattern: Balmer had discovered in 1885
that the emitted wavelengths follow the empirical law, =
0
(1/4 1/n
2
)
where n = 3, 4, 5, and
0
= 3645.6

A (see Fig. 1.4). Neils Bohr realized

that these discrete vaues of the wavelength reected the emission of individual
photons having energy equal to the energy dierence between two allowed
orbits of the electron circling the nucleus (the proton), E
n
E
m
= h, leading
to the conclusion that the allowed energy levels must be quantized and varying
as E
n
=
hcR
H
n
2
, where R
H
= 109678 cm
1
denotes the Rydberg constant.
3
Classically, light of sucient intensity for the electric eld to accelerate a charged particle
to a relativistic speed will cause radiation-pressure recoil and an associated Doppler shift of
the scattered light. But the eect would become arbitrarily small at suciently low light
intensities regardless of wavelength.
4
If we assume that the total energy and momentum are conserved in the scattering of a
photon () from an initially stationary target electron (e), we have E + Ee = E

+ E
e

and p = p

+ p
e
. Here E = h and Ee = mec
2
denote the energy of the photon
and electron before the collision, while E

= h

and E
e
=
p
(p
e
c)
2
+ (mc
2
)
2
denote the
energies after. From the equation for energy conservation, one obtains (p
e
c)
2
= (h(

) + mec
2
)
2
(mec
2
)
2
. From the equation for momentum conservation, one obtains p
2
e
=
p
2

+ p
2

2|p||p

| cos . Then, noting that E = pc, a rearrangement of these equations

obtains the Compton scattering formula.
Advanced Quantum Physics
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 h restricting allowed radiation energies also re-
strict the allowed electron orbits? In 1913 Bohr proposed that the angular
momentum of an electron in one of these orbits was quantized in units of
Plancks constant,
L = m
e
vr = n, =
h
2
. (1.2)
As a result, one nds that R
H
= (
e
2
4
0
)
2 2
2
m
ch
3
.
Niels Henrik David Bohr 1885-
1962
A Danish physi-
cist who made
fundamental
contributions
to the un-
derstanding
atomic structure
and quantum
mechanics, for
which he received
the Nobel Prize in Physics in 1922.
Bohr mentored and collaborated
with many of the top physicists
of the century at his institute in
Copenhagen. He was also part of the
team of physicists working on the
Manhattan Project. Bohr married
Margrethe Norlund in 1912, and one
of their sons, Aage Niels Bohr, grew
up to be an important physicist who,
like his father, received the Nobel
prize, in 1975.
Exercise. Starting with the Bohrs planetary model for atomic hydrogen,
nd how the quantization condition (1.2) restricts the radius of the allowed (circular)
orbits. Determine the allowed energy levels and obtain the expression for the Rydberg
constant above.
But why should only certain angular momenta be allowed for the circling
electron? A heuristic explanation was provided by de Broglie: just as the
constituents of light waves (photons) are seen through Compton scattering
to act like particles (of denite energy and momentum), so particles such as
electrons may exhibit wave-like properties. For photons, we have seen that
the relationship between wavelength and momentum is p = h/. de Broglie
hypothesized that the inverse was true: for particles with a momentum p, the
wavelength is
=
h
p
, i.e. p = k , (1.3)
where k denotes the wavevector of the particle. Applied to the electron in
Louis Victor Pierre Raymond,
7th duc de Broglie 1892-1987
A French physi-
cist, de Broglie
had a mind of
a theoretician
rather than
one of an
experimenter
or engineer.
de Broglies
1924 doctoral
thesis Recherches sur la theorie des
quanta introduced his theory of
electron waves. This included the
particle-wave property duality theory
of matter, based on the work of
Einstein and Planck. He won the
Nobel Prize in Physics in 1929 for
his discovery of the wave nature of
electrons, known as the de Broglie
hypothesis or mecanique ondulatoire.
the atom, this result suggested that the allowed circular orbits are standing
waves, from which Bohrs angular momentum quantization follows. The de
Broglie hypothesis found quantitative support in an experiment by Davisson
and Germer, and independently by G. P. Thomson in 1927. Their studies
of electron diraction from a crystalline array of Nickel atoms (Fig. 1.5) con-
rmed that the diraction angles depend on the incident energy (and therefore
momentum).
This completes the summary of the pivotal conceptual insights that paved
the way towards the development of quantum mechanics.
Advanced Quantum Physics
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 dened as the incident beam. The phenomenological similarities
with X-ray diraction were striking, and showed that a wavelength could indeed be
associated with the electrons. The rst gure shows the intensity of electron scattering
against co-latitude angle for various bombarding voltages. The second gure shows
the intensity of electron scattering vs. azimuth angle - 54V, co-latitude 50. Figures
taken taken from C. Davisson and L. H. Germer, Reection of electrons by a crystal
of nickel, Nature 119, 558 (1927).
1.2 Wave mechanics
de Broglies 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
Schrodinger that he give a seminar on de Broglies work. Schrodinger gave a
polished presentation, but at the end, Debye remarked that he considered the
whole theory rather childish: Why should a wave conne itself to a circle in
space? It wasnt as if the circle was a waving circular string; real waves in space
diracted and diused; in fact they obeyed three-dimensional wave equations,
and that was what was needed. This was a direct challenge to Schrodinger,
who spent some weeks in the Swiss mountains working on the problem, and
constructing his equation.
There is no rigorous derivation of Schrodingers equation from previously
established theory, but it can be made very plausible by thinking about the
connection between light waves and photons, and constructing an analogous
structure for de Broglies waves and electrons (and, of course, other particles).
1.2.1 Maxwells wave equation
James Clerk Maxwell 1831-1879
was a Scottish
theoretical
physicist and
mathematician.
His greatest
achievement was
the development
of classical
electromagnetic
theory, synthesizing all previous
unrelated observations of electric-
ity, magnetism and optics into
a consistent theory. Maxwells
equations demonstrated that elec-
tricity, magnetism and light are all
manifestations of electromagnetic
eld.
For a monochromatic wave in vacuum, with no currents or charges present,
Maxwells wave equation,

2
E
1
c
2

E = 0 , (1.4)
admits the plane wave solution, E = E
0
e
i(krt)
, with the linear dispersion
relation = c|k| and c the velocity of light. Here, (and throughout the text)
we adopt the convention,

E
2
t
E. We know from the photoelectric eect
and Compton scattering that the photon energy and momentum are related
to the frequency and wavelength of light through the relations E = h = ,
p =
h

= k. The wave equation tells us that = c|k| and hence E = c|p|.

If we think of e
i(krt)
as describing a particle (photon) it would be more
natural to write the plane wave in terms of the energy and momentum of the
Advanced Quantum Physics
1.2. WAVE MECHANICS 7
particle as E
0
e
i(prEt)/
. 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 m
0
. We require
a wave equation that, when it operates on a plane wave, yields the relativis-
tic energy-momentum invariant, E
2
= (cp)
2
+ m
2
0
c
4
. Writing the plane wave
function (r, t) = Ae
i(prEt)/
, where A is a constant, we can recover the
energy-momentum invariant by adding a constant mass term to the wave op-
erator,
_

2
t
c
2

m
2
0
c
2

2
_
e
i(prEt)/
=
_
(cp)
2
E
2
+ m
2
0
c
4
_
(c)
2
e
i(prEt)/
= 0 .
This wave equation is called the Klein-Gordon equation and correctly de-
scribes the propagation of relativistic particles of mass m
0
. 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 (x, t) =
Ae
i(prEt)/
. We need to construct an operator which, when applied to this
wave function, just gives us the ordinary non-relativistic energy-momentum
relation, E =
p
2
2m
. The factor of p
2
can obviously be recovered from two
derivatives with respect to r, but the only way we can get E is by having a
single dierentiation with respect to time, i.e.
i
t
(r, t) =

2
2m

2
(r, t) .
This is Schrodingers 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 eect
the propagation of a de Broglie wave? This question was considered by Som-
merfeld in an attempt to generalize the rather restrictive conditions in Bohrs
model of the atom. Since the electron orbit was established by an inverse-
square force law, just like the planets around the Sun, Sommerfeld couldnt
understand why Bohrs atom had only circular orbits as opposed to Kepler-
like elliptical orbits. (Recall that all of the observed spectral lines of hydrogen
were accounted for by energy dierences between circular orbits.)
Arnold Johannes Wilhelm Som-
merfeld 1868-1951
A German the-
oretical physicist
who pioneered
developments
in atomic
and quantum
physics, and also
educated and
groomed a large
number of students for the new era
of theoretical physics. He introduced
the ne-structure constant into
quantum mechanics.
de Broglies analysis of the allowed circular orbits can be formulated by
assuming that, at some instant, the spatial variation of the wavefunction on
going around the orbit includes a phase term of the form e
ipq/
, where here
the parameter q measures the spatial distance around the orbit. Now, for an
acceptable wavefunction, the total phase change on going around the orbit
must be 2n, 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/ 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 pq/. Requiring the wavefunction to
link up smoothly on going once around the orbit gives the Bohr-Sommerfeld
Advanced Quantum Physics
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 Bohrs 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 Sommerfelds result for the
elliptical orbit.
1.2.2 Schrodingers equation
Following Sommerfelds 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 thats where the particle is going the fastest. Our task then is to
construct a wave equation which leads naturally to the relation following from
(classical) energy conservation, E =
p
2
2m
+V (x). In contrast to the free particle
case discussed above, the relevant wavefunction here will no longer be a simple
plane wave, since the wavelength (determined through the momentum via the
de Broglie relation) varies with the potential. However, at a given position
x, the momentum is determined by the local wavelength. The appropriate
wave equation is the one-dimensional Schrodinger equation,
Erwin Rudolf Josef Alexander
Schrdinger 1887-1961
was an Austrian
theoretical
physicist who
achieved fame
for his contribu-
tions to quantum
mechanics,
especially the
Schrodinger
equation, for
which he received the Nobel Prize
in 1933. In 1935, after extensive
correspondence with personal
friend Albert Einstein, he proposed
the Schrodingers cat thought
experiment.
i
t
(x, t) =

2
x
2m
(x, t) + V (x)(x, t) , (1.6)
with the generalization to three-dimensions leading to the Laplacian operator
in place of
2
x
(cf. Maxwells equation).
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? Schrodingers test of his equation was the hydrogen atom. He looked
for Bohrs stationary states: states in which the electron was localized some-
where near the proton, and having a denite energy. The time dependence
would be the same as for a plane wave of denite 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 Schrodinger equation
As with all second order linear dierential equations, if the potential V (x, t) =
V (x) is time-independent, the time-dependence of the wavefunction can be
Advanced Quantum Physics
1.2. WAVE MECHANICS 9
separated from the spatial dependence. Setting (x, t) = T(t)(x), and sep-
arating the variables, the Schrodinger equation takes the form,
_

2
x
2m
(x) + V (x)(x)
_
(x)
=
i
t
T(t)
T(t)
= const. = E .
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 Schrodinger
equation,

2
x
2m
(x) + V (x)(x) = E(x) .
The full time-dependent solution is given by (x, t) = e
iEt/
(x) with def-
inite energy, E. Their probability density |(x, t)|
2
= |(x)|
2
is constant in
time hence they are called stationary states! The operator

H =

2
x
2m
+ V (x)
denes the Hamiltonian and the stationary wave equation can be written as
the eigenfunction equation,

H(x) = E(x), i.e. (x) is an eigenstate of

H
with eigenvalue E.
1.2.4 Particle ux and conservation of probability
In analogy to the Poynting vector for the electromagnetic eld, 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 ow along the
direction of momentum. We can derive an equation showing conservation of
probability by dierentiating the probability density, P(x, t) = |(x, t)|
2
, and
using the Schrodinger equation,
t
P(x, t)+
x
j(x, t) = 0. This translates to the
usual conservation equation if j(x, t) is identied as the probability current,
j(x, t) =
i
2m
[

x

x

] . (1.7)
If we integrate over some interval in x,
_
b
a

t
P(x, t)dx =
_
b
a

x
j(x, t)dx it
follows that
t
_
b
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 ux 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 ux,
j(r, t) =
i
2m
[

(r, t)(r, t) (r, t)

(r, t)] . (1.8)

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 Schrodinger 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.
Advanced Quantum Physics