Physics 251a

Advanced Quantum Mechanics I

Prof. Cumrun Vafa
Typesetting: Yichen Shi

Fall 2014, Harvard University

Last updated: December 6, 2014

These are the lecture notes from Professor Cumrun Vafa’s graduate level Quantum Mechanics course given in Fall
2014, at Harvard University. If you find errors or have any question, please send an email to [email protected].

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Contents
1 The History of Quantum Mechanics and Motivation 4
1.1 1900, Rayleigh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 1900, Planck . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 1910, Lorentz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4 1905, Einstein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.5 1922, Compton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.6 1909-1911, Rutherford . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.7 1913, Bohr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.8 1916, Sommerfeld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.9 1916, Einstein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.10 1923, de Broglie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.11 1923, Schrödinger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.12 1925, Heisenberg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.13 1926, Born, Heisenberg, Jordan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.14 1927, Ehrenfest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.15 Probabilistic Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2 Radially Symmetric Problems 17

2.1 The Hydrogen Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2 The Laplacian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 L2 and Lz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4 Spherical Harmonics Ylm (θ, φ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.5 The Radial Part R(r) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.6 Decay Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.7 The Two-Body Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.8 Three-Dimensional Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

3 Principles of Quantum Mechanics 32

3.1 Preliminaries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2 Principles of Quantum Mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

4 Spins 48
4.1 Addition of Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.2 Identical Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.3 Electrons and the Nucleus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.4 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.5 Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.6 Wigner-Eckart Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.6.1 Tensorial Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.6.2 Isospin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.7 Discrete Symmetries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.8 Supersymmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

5 Time-independent Perturbation Theory 64

5.1 Non-Degenerate Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.2 Degenerate Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.2.1 Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.2.2 Stark Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.3 Variational Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.3.1 Virial Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.4 Bohn-Oppenheimer Approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.5 WKB Approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.5.1 Bohr-Sommerfeld Quantisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.5.2 Barrier Penetration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

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6 Time-dependent Perturbation Theory 76
6.1 Sudden Time-Dependence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.2 H = H0 + H 0 (t) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.2.1 Hydrogen Atom Ionisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.3 Fluctuating Perturbation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.3.1 Radiation Absorption and Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6.4 Adiabatic Perturbation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6.5 Berry’s Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

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1 The History of Quantum Mechanics and Motivation

Quantum mechanics started almost exactly in 1900. It started with the explanation of the distributions of
intensities that we obtain in the context of radiations.

1.1 1900, Rayleigh

Lord Rayleigh tried to apply simple ideas from statistical mechanics to radiation interacting with matter. In the
context of statistical mechanics, we study basic configurations of particles where for each independent configuration,
we get some energy related to the Boltzmann constant, i.e., to the temperature. We can thus study the intensity
of radiation. In particular, we have some energy density per unit frequency at a given temperature, ρ(ν, T ), i.e.,

ρ(ν, T )dν = energy per unit volume in the frequency range ν and ν + dν at temperature T.

Lord Rayleigh wanted to compute ρ(ν, T ). He started with some cubic box with all sides heated up to temper-
ature T . The temperature excites some radiation, i.e., creates some electromagnetic fields. So how much energy,
or what kind of frequencies, do we see in this situation? If we take all possible modes, then each mode gives us the
energy of 21 kT by Boltzmann’s rule.

To find the electromagnetic modes in a box, assume that the box is periodic for simplicity, i.e., we identify the
front and the back, the left and the right, and the top and the bottom sides. Let the box have length L. We can
take the standard form of electromagnetic waves

~ ∼ ~v ei(~k·~x−ωt) ,
E

where ~k = 2π
L~ n. The allowed modes are such that ~k takes normal mode values because of the periodic boundary
conditions. If we shift x by L in any direction, this guarantees that it comes back to itself.

Now, we want to associate these modes. Take a coordinate system with axes labelled by nx , ny , nz . We have
all the integer points in space representing the modes and they don’t all have the same frequency.

What is the relation among their frequencies? We have the angular frequency

ω = 2πν = |~k|c.

Hence,
|~k|c |~n|c
ν= = .
2π L
If we want to look at a particular frequency, take a spherical shell with a particular radius, say |~n|, in the space.
Then all particles on the sphere have the same frequency. But the shell is too thin to contain any particles! So we
are interested in a particular frequency range, i.e., in the number of modes lying on a shell with some thickness.

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 We’ll first calculate how many modes there are, then use the equipartition theorem from statistical mechanics
to see how much energy each one of them has. The assumption is that L is sufficiently big that this is almost a
continuum. To count one mode per unit cell, write
 2
2 νL L
dnx dny dnz = 4πn d|~n| = 4π dν,
c c

and the number of modes in the shell

4πν 2 3
dN = 2 L dν,
c3
where the 2 is due to the two polarisations for each mode. So the number of modes per unit volume

dN 8πν 2
= 2 dν.
V c
This is the kinematics of the number of modes. Next, how much energy does each mode have? Think of the
modes as oscillators with kinetic and potential parts. According to the equipartition theorem, we have
1 1
Ē = kT + kT = kT
2 2
for each mode. Hence
ĒdN 8πν 2
ρ(ν, T ) = = 3 kT.
V dν c
But wait a minute, we have infinitely many modes! If each one of them has energy kT , then the total energy is
infinity! Z ∞
E
= ρ(ν)dν = ∞.
V 0
It’s not that both statistical mechanics and normal modes don’t work, but that there is another part to the
story.

1.2 1900, Planck

Experimentally, if we plot ρ against ν, the curve comes back down smoothly to zero instead of shooting up to
infinity.

Planck looked at the curve and guessed

ν3#
ρ∼ ,
e#ν − 1
where the denominator comes from the fact that the curve becomes exponentially suppressed for large ν, and
because Rayleigh’s ρ ∝ ν 2 works for small frequencies, the ν 3 is to cancel the factor of ν in the denominator for
small ν, in order to produce ν 2 .

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 Now, kT is energy, ν is frequency. How can we get energy out of frequency? We can multiply ν/kT by some
constant to make it dimensionless. Let’s call the constant h, such that

[h] = energy × time.

So he arrived at
8πhν 3
ρ(ν) = .
c3 ( ehν/kT − 1)
Notice that ehν/kT − 1 → hν/kT as ν → 0, i.e., it matches with Rayleigh’s conclusion for small frequencies.

h is then experimentally measured to have the value 6.6 × 10−27 erg sec (using cgs units).

A few months later, Planck wrote another paper to derive the same formula using the assumption that matter
only absorbs or emits radiation in particular chunks proportional to hν.

These exciting discoveries led to the measurement of the Boltzmann constant k, and in turn, the computation
of Avogadro’s number NA (through R = kNA , since P V = nRT = NA kT ), the electric charge e (through eNA
measured by Faraday), me (through m e ~ field in
from the bending of the electron streams in the presence of the B
the Cathode Ray).

1.3 1910, Lorentz

Based on Einstein’s work, Lorentz assumed that not only matter comes in chunks proportional to hν, but also
electromagnetic radiation. Planck’s formula is correct, but something is wrong with the factor of kT . He started
with the fact that the probability to be in any particular state of a given energy E is proportional to e−E/kT . Since
energy comes in discrete chunks, we count each state easily and the probability to be in a particular state with n
units
e−nhν/kT
P (n) = P∞ −mhν/kT
,
m=0 e
and the energy of the unit P∞ −nhν/kT
n=0 nhν e
X
Ē = Ēn = P∞ −mhν/kT
.
m=0 e
Now,
∞
X 1
e−nx = .
n=0
1 − e−x
Hence,
∞
X ∂ 1 e−x
n e−nx = − −x
= .
n=0
∂x 1 − e (1 − e−x )2
Hence the average energy
hν e−hν/kT hν
Ē = = hν/kT ,
1 − e−hν/kT e −1
which approaches kT as ν → 0.

As we can see, the chunkiness doesn’t matter for small frequencies but does for large ones. It makes sense since
for hν  kT , it’s such a tiny quantity that we seem to have a continuum.

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1.4 1905, Einstein

Einstein’s photoelectric effect involves shining light to the copper attached to one end of a circuit. As a result,
the electrons in the copper would be hit, and we can register a current in the circuit. So what is the voltage we
need to stop the current? Vstop as a function of ν of the light starts at some νmin and increases linearly.

Notice that it has nothing to do with intensity. Classically, when intensity goes up, energy goes up, and the
electrons which absorbed energy should start moving. So it’s strange that up to νmin , no current is registered. The
Vstop is only proportional to ν.

Einstein had a basic explanation of it, based on the assumption that radiation also comes in chunks. The
electrons are bounded by some potential, so to get them out, we need some minimum energy Emin = hνmin , which
is the energy of binding of electrons inside the copper. And if we have some more energy more than the minimum,
then that should translate to energy of the electron that’s free. Hence

hν − hνmin = eVstop .

1.5 1922, Compton

Let’s shine light with frequency ν on an electron at rest. Classically, we expect that the radiation coming back
to have the same frequency. But that is not the case. Again, the chunkiness in the energy of the electromagnetic
radiation was included in the explanation.

Think of light as a particle with energy E = hν. In Einstein’s theory, it’s clear that if it were a particle which
goes at the speed of light, then we’d be in trouble, since we’d need infinite energy. The only resolution is for it to
be a massless particle.
m2γ
H
 Hc4 = E 2 − p2 c2 .

H
⇒ E = |~
p|c.
Take light hiting the electron at rest with ν and coming right back at us with ν 0 . The electron picks up
momentum pe . With no computation at all, it is clear that ν 0 < ν. Momentum conservation gives

hν 0 hν
pe − = ,
c c
i.e.,
h
pe = (ν − ν 0 ).
c
Energy conservation gives p
hν + me c2 = hν 0 + (me c2 )2 + h2 (ν + ν 0 )2 ,
i.e.,
me c2
ν0 = ν,
2hν + me c2

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which approaches ν as h → 0, i.e., in the classical limit. From c = λν,
2h
λ0 = + λ.
me c

Note that mhe c ∼ 2.4 × 10−10 cm is the Compton wavelength of electrons. So for particles, we can associate some
kind of length. Note that now we also have

[h] = length × momentum.

1.6 1909-1911, Rutherford

We used to think that matter was of jelly-type having electrons with negative charges stuck inside. We assumed
that the jelly has some positive charge density to cancel the negative charges.

Rutherford then did a revolutionary experiment, where he shot α++ particles (Helium nucleus) at this “jelly”
of gold. He expected that the α++ ’s would go straight through. To his surprise, some did not, and some even came
back at him! So this directly implied that the positive charge density, that matter, should be localised. So if the
kinetic energy of the alpha particles can be cancelled by the potential energy, then
1 2eZe
mv 2 ∼ ,
2 r
where we have 2e because the α++ ’s are doubly positively charged, Z ∼ 100, and r ∼ 3Z × 10−14 cm. So he was
able to measure the size of the nucleus of gold.

However, when charged objects rotate around other charged objects, they radiate energy, and decay. So the
orbit becomes smaller and smaller and goes away. And we can easily estimate the time for it to disappear altogether!
So this picture is inconsistent.

1.7 1913, Bohr

Now, Bohr thought that if radiation is chunky, then matter might be chunky too. The electrons can only go on
special orbits. What if angular momentum also comes in chunks? That would explain the specific radii allowed.
So suppose
l = rp = n~,
where ~ is some constant with the same units as h. They’re probably related!

An electron from a higher orbit can jump to a lower one, by emitting some energy cancelling the difference
between the two energies corresponding to the two orbits. Hence,

−Ef + Ei = hνi→f .

So what are the allowed energies? Assume that we have Z units of positive charges here, and electrons are
going around it in circle.
mv 2 Ze2 p2 r
= 2 ⇒ = Ze2 .
r r m
But we also have rp = n~. So we have
n 2 ~2
r= .
Ze2 m

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 Hence,

1 Ze2
En = mv 2 −
2 r
Ze2
=−
2r
Z 2 e4 m 1
=− .
2~2 n2
And for Z = 1,
1
En = −13.6 eV.
n2
To find the relation between ~ and h, we go back to the situation where an electron jumped down an orbit,
emitting a photon of frequency νi→f .
" #
1 1
Ei − Ef = hνi→f = −const. 2 − 2 ,
ni nf

from which we can deduce the spectral lines. We can then use it to compute ~. We do find a difference of a factor
of 2π, but that’s not satisfying enough.

Another way to go about it is to use classical results. Of course, quantum mechanics should be reducible to
classical mechanics. Here, for large n, orbits become closer together and we approach the classical continuum. We
would expect that jumping from one orbit to the one lower corresponds to some ν which matches the frequency of
the classical orbit.

First note that for n  1,

1 1 2
2
− 2 ' − 3.
(n + 1) n n
Now, say we go from n + 1 to n. Then

Z 2 e4 m Z 2 e4 m 1
 
1 1
En+1 − En = − − ' ' hνn ,
2~2 (n + 1)2 n2 ~2 n 3

for n  1. In classical physics,

p v 1
= = = ν,
2πmr 2πr T
which gives
n~ n~ mZ 2 e4
νn = = 4 4 = .
2πmr2 2πm Zn2 e4~m2 2πn3 ~3

Hence
hmZ 2 e4
hνn = .
2πn3 ~3
Now when we match the results above, we get
h
= 1.
2π~
Note that
n2
r= 0.5 × 10−8 cm;
Z
p n~ 1 Zc e2 1
v= = = , = .
m mr 137 n ~c 137
We know that the speed of electron isn’t the speed of light, so Z  137 is required for this formula to work.

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1.8 1916, Sommerfeld

Consider electrons going around orbits. We have

I
p dx = 2πrp = 2πn~ = nh.

If we look at a classical trajectory in a phase space given by x an p, integral around an orbit is the same as
computing the area bounded inside the classical trajectory, i.e.,
I ZZ
p dx = dxdp = nh.
A

So the formula is saying that if we have some classical orbit, the area is quantised in units of h. At some point,
they thought that this Bohr-Sommerfeld quantisation rule might be the principle of quantum mechanics. Now we
know that this is just an approximate statement.

By that time, physicists have invented the Hamiltonian formulation of classical physics, in terms of positions
and momenta. Here is a quick reminder of it. With the Hamiltonian

p2
H= + V (x),
2m
we have
∂H dxi dx p
= , = ;
∂pi dt dt m
∂H dpi dp dV
i
=− , =− = F.
∂x dt dt dx
The first order differential equations can be very useful.

1.9 1916, Einstein

We know that an electron can jump from an orbit of higher energy to a lower one by emitting radiation. How
do we compute the rate of this decay? If there’s a hydrogen atom in an excited state, how long does it take for it
to jump down? Let’s call the decay rate from the higher orbit m to the lower one, n, Am n .

Einstein, while working on his relativity, had the following remarkable idea. Suppose we put an atom in a
thermal bath of radiation. Then the reverse process is possible: electrons can jump from the lower energy state n
to the upper, m, because of the radiation around. In fact, it’d better be the case since otherwise we won’t have
statistical equilibrium. The number of particles in state m, Nm , compared to that in state n, Nn , is given by

Nm e−Em /kT (Em −En )

= −E /kT = e− kT .
Nn e n
The decay rate should depend on the density of the radiation around. The frequency νmn of the photon the
electron needs to absorb to jump up is
Em − En
νmn = .
n
Then the spontaneous emission
Γspon m
n→m = Bn ρ(νmn ),

for some constant Bn m . Now, the decay from m to n, which we assigned Am n to, can happen even without
radiation. But if there was radiation, would we get something extra? Let’s suppose that the stimulated emission

Γsti n
m→n = Bm ρ(νmn ),

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for some different constant Bm n .

We now have three unknowns: Am n , Bn m , and Bm n , but notice that in equilibrium, the number of particles
going from n to m should be the same as that going from m to n. The number of particles that goes from m to
n per unit time is Nm multiplied by the sum of the two sources of emission, and he number of particles that goes
from n to m per unit time is Nn multiplied by the single source. Hence,

Nm (Am n + Bm n )ρ(νmn ) = Nn (Bn m ρ(νmn )).

Using our expressions for Nm /Nn , νmn , and recall

8πh ν3
ρ(ν, T ) = 3 hν/kT
.
c e −1
Then we have  8πh 3
 νnm
Am n = ehνnm /kT Bn m − Bm n .
−1 c3 e nm /kT
hν

Notice that the rate of emission should be temperature independent. It can occur at all temperature! So the
temperature dependence in the denominator should be cancelled by the numerator. Hence

Bn m = Bm n ,

and in turn,
3
8πhνnm
Am n = B m n 3
.
c
These are called the Einstein’s A and B coefficients.

1.10 1923, de Broglie

So waves are particles. How about the reverse? de Broglie started with Planck’s relations

E = |~
p|c,
~
which is what we expect since the photon is massless. We can have a wave ∼ ei(k·~x−ωt) . And we also have,

E = ~ω, p~ = ~~k.

Let’s assume these for particles! But ω = c|~k| doesn’t work here since

ω ~ω E p2 /2m |~
p| p
= = = = 6= .
~
|k| ~
~|k| |~
p | |~
p | 2m m

But wave packets have a group velocity! Say we have a wave packet
Z
ψ(~x, t) = ei(kx−ω(k)t) φ(k)dk.

We expand around k0 .
Z dω(k)

i(k0 x−ω(k0 ))t i(x− dk t )k0 (k−k0 )
ψ(~x, t) = e e φ(k)dk
 !
dω(k) 
= ei(k0 x−ω(k0 ))t f x− t
dk k0

The phase is unimportant. So this is a wave packet which moves with velocity
∂ω ∂(~ω) ∂E p
v= = = = .
∂k ∂~k ∂p m

11
 Hence it works out if we use the group velocity. So why does the Bohr-Sommerfeld quantisation work? Suppose
that we have a particle going around some orbit. Of course, the particle is associated with some wavefunction. But
the wave is a single-valued function of position. The phase at each point is eikx , so the change in phase after we
have gone all the way around should be
i
R R
ei k dx = e ~ p dx = 1.
Hence, Z
p dx = 2πn~ = nh.

The fact that we get integer quantum numbers is analogous to the normal modes of the standing waves in a
box, characterised by integers. So the concept of waves explains it all.

1.11 1923, Schrödinger

Schrödinger thought, then expressing p~ as some gradient would bring down a factor of ~k from some plane wave
to satisfy p~ = h~k. Similarly, expressing E as some time derivative will bring down a factor of ω to satisfy E = ~ω.
Hence,
∂ ∂
−i~ ψ = p~ψ; i~ ψ = Eψ;
∂x ∂t
So replace
∂
p~ → i~∇; E → i~
∂t
to solve problems! Starting with
p2
H= + V (~x),
2m
we immediately arrive at the Schrödinger equation

(−i~∇2 )
i~ = + V (~x)ψ.
2m
For many particles, simply write the Hamiltonian as
N
X p2i
H= + V (~xi ),
i=1
2mi

and take
ψ = ψ(~x1 , ..., ~xN , t).
Now we can write down any problem in classical mechanics in terms of the wave equation! It was solved for the
Hydrogen atom, giving the same spectrum as the one Bohr arrived at using heuristic arguments.

12
1.12 1925, Heisenberg

Unlike Schrödinger, Heisenberg didn’t think of the “waves” as the ordinary kind of waves. Suppose a particle
is having a transition from energy state m to n. We expect the power of radiation formula
2e2 ẍ2
P =
3c3
to work. But there are two orbits. By “x”, which one are we referring to? The notion of position should depend
on both n and m. Suppose we are going from m to n to k, then we have to have some product of m to n with n
to k. So we should have X
x2mk = xmn xnk ,
n
now called matrix multiplication. Since we are dealing with matrices, order of multiplication matters, and we have
xp − px = i~1 6= 0.
The Hamiltonian, which gives a definite value, should be a diagonal matrix.
[H(x, p)]nm = δnm En .
He used this definition of energy and the fact that x and p don’t commute to solve the Harmonic oscillator,
without any discussion of waves. He found that with
p2 1
H= + kx2 ,
2m 2
the energy eigenstates are r
 
1 k
En = n+ ~ω, ω= , n = 0, 1, 2, ...
2 m
The Heisenberg and the Schrödinger formulations are equivalent in the context of wavefunction being a function
of ~x and t only. We now know that there are other components to quantum mechanics, the quantum numbers such
as the spin, which are not captured by ~x and t. So the Schrödinger formulation is inadequate. Heisenberg’s way of
thinking is more general, and he was correct by considering an abstract space: We can talk about matrices of spin.

Let’s quickly review Schrödinger’s approach. He started with

Hψn (~x, t) = En ψn (~x, t)
And he defined inner products Z
hψ|φi = ψ ∗ (~x, t)φ(~x, t) d3 x,

and Z
hψ|ψi = |ψ|2 d3 x

is a positive definite quantity. Then the Heisenberg matrices, written in terms of Schrödinger’s approach, are
Z
∗
xmn = ψm (~x, t)xφn (~x, t) d3 x.

The statement of matrix multiplication

X
(x2 )mk = xmn xnk
n

makes sense turns out to be a statement about the completeness of space of eigenfunctions. Notice that
Z Z
∗ ∗
ψm (~x, t)(xp − px)ψn (~x, t) d3 x = i~ ψm ψn d3 x.

So for anything we’re computing, we can replace xp − px with i~.

13
1.13 1926, Born, Heisenberg, Jordan

We can write the Hamiltonian in terms of mode expansions as

X 
H= ȧ~2k + ω~k2 a~2k .
~
k

This is basically an infinite set of Harmonic oscillators already solved by Heisenberg. The energy
 
1
E = N~k + ~ω,
2

where the N is the level of excitation. But what is the meaning of the wavefunction ψ(~x, t)? Schrödinger knew that
the energy is proportional to |ψ(~x, t)|2 . So ψ(~x, t) somehow represents the amount of wave. He made an obvious
statement that
|ψ(~x, t)|2 = the amount of particle at ~x, t.
But Bohr pointed out the caveat that as time goes on, waves spread out to infinity. So are you telling me that
the particle at a later time is everywhere? We actually measure the particle at one place only! So the interpretation
came after the formulation of quantum mechanics. How about the probability instead of the “amount”? i.e.,

|ψ(~x, t)|2 = the probability density for a particle to be found at ~x, t,

or,
|ψ(~x, t)|2 d3 x = the probability for a particle to be in the volume element d3 x.
This is the probabilistic interpretation of quantum mechanics. Suddenly, probability came into physics! Even
today, the interpretation of quantum mechanics is still controversial.

Now, regarding probabilities, we know that the average value of some quantity O,
X
hOi = Pi O i .
i

Hence, Z
hf (x)i = |ψ|2 f (~x) d3 x.

Of course, a particle must be somewhere. So we have the normalisation condition

Z
|ψ(~x, 0)|2 f (~x) d3 x = 1.

It’d better be the case that the probability doesn’t change in time, i.e.,
Z
|ψ(~x, t)|2 f (~x) d3 x = 1.

In other words, we require that

Z Z    
d 2 3 ∂ ∗ ∗ ∂
|ψ| d x = ψ ψ+ψ ψ d3 x = 0.
dt ∂t ∂t
Notice that
~2 2
 
∂
− ∇ + V ψ = i~ ψ;
2m ∂t
2
 
~ ∂
− ∇2 + V ψ ∗ = −i~ ψ ∗ .
2m ∂t
The potential cannot be complex since the energy is real. So we have
Z Z  
d 2 3 ~ 2 ∗ ∗ ~
|ψ| d x = (∇ ψ )ψ − ψ ∇ ψ d3 x.
2
dt 2im 2im

14
 But since the wavefunction is normalised, the ψ at infinity vanishes. So we can use integration by parts to
obtain Z Z  
d ~ ~
|ψ|2 d3 x = − (∇ψ ∗ )∇ψ + (∇ψ ∗ ) ∇ψ d3 x = 0.
dt 2im 2im

1.14 1927, Ehrenfest

Ehrenfest started with an easy computation. For O with no explicit time dependence,

Hψ ∗ Oψ ψ ∗ OHψ 3
Z Z   Z
d d 1
hOi = ψ ∗ Oψ d3 x = + d x= [−ψ ∗ H(Oψ) + ψ ∗ OHψ] .
dt dt −i~ i~ i~

We introduce here the commutator

[A, B] = AB − BA.
Hence we can write
d hOi
Z
1
= ψ ∗ [O, H]ψ,
dt i~
or,
d hOi 1
= h[O, H]i .
dt i~
So the rate at which the average of a quantity changes depend on the average value of its commutator with the
Hamiltonian. If O was time-dependent, then
 
d hOi 1 ∂O
= h[O, H]i + .
dt i~ ∂t

This is known as the Ehrenfest theorem. It’s basically the statement that if something commutes with the
Hamiltonian, it’s a conserved quantity. So the Hamiltonian tells us what doesn’t change with time: it is a generator
of time translations. We can think of the time derivative as being replaced as
d 1
· 7→ [ · , H].
dt i~
Here are the properties of the commutator.

[A, B] = −[B, A];

[A, λB] = λ[A, B];

[A, B + C] = A(B + C) − (B + C)A = [A, B] + [A, C];
[A, BC] = ABC − BAC + BAC − BCA = [A, B]C + B[A, C].
Now,
∂ ∂
ψ ∗ [x, p]ψ = ψ ∗ x(−i~) ψ + i~ (xψ) = i~.
∂x ∂x
We work in one-dimension for simplicity. Using the Ehrenfest theorem, we have

d hxi 1
= h[x, H]i
dt i~ 
p2

1
= [x, ] +
[x,V
(x)]

i~ 2m
1 1
= h[x, p]p + p[x, p]i
i~ 2m
hpi
= .
m

15
 Now, Z      
∗ ∂ ∂ dV
h[p, V (x)]i = ψ −i~ (V ψ) − V −i~ ψ dx = −i~ .
∂x ∂x dx
Similarly,
d hpi 1
= h[p, H]i
dt i~
1
= h[p, V (x)]i
i~ 
dV
=− .
dx
So we have recovered Newton’s laws in an average sense. Satisfying Schrödinger equation implies that things
work, in an average sense.

1.15 Probabilistic Interpretation

First, here’s a note on our notation.

Z
hψ, φi = hψ|φi = ψ ∗ φ d3 x;

We’ll stick with physicists’ Dirac notation hψ|φi instead of the mathematicians’ hψ, φi notation in this class.
Notice that
hψ|φi = hφ|ψi.
So for a physical operator O, hOi being real implies
Z Z
!
ψ ∗ Oψ d3 x = hψ|O|ψi = hψ|O|ψi = ψ ∗ O∗ ψ d3 x.

We thus have the definition of a Hermitian operator. An operator A is Hermitian if, in mathematicians’ notation,
∗ !
hφ, Aψi = hAψ, φi = hψ, Aφi ,
or in physicists’ notation (which could be confusing as to which side A acts on),
!
hφ|A|ψi = hψ|A|φi .
So for real expectation values, we must have Hermitian operators correspondingly.

Now, suppose A = a for a particular wavefunction, where a is some number, an outcome of some measurement.
Then computations of the deviation of A in that state is zero. But that just means that the average is zero, i.e.,
hA − ai = 0.
The expectation value of any powers of (A − a) must also be zero in that particular state. Let’s see the
implications of
(A − a)2 = 0.



We have, noting again that A is Hermitian and a is real,

0 = ψ|(A − a)2 |ψ


Z
= ψ ∗ (A − a)(A − a)ψ d3 x
Z
= [(A − a)ψ]∗ (A − a)ψ d3 x
Z
≡ φ∗ φ d3 x.

16
 So the integrand must be zero, i.e.,
|φ|2 = 0.
Hence, (A − a)ψ = 0, or,
Aψ = aψ,
i.e., ψ is an eigenvector of A with eigenvalue a. The only values that we can possibly measure are these eigenvalues.
For every Hermitian A, we can expand ψ as a linear combination of eigenstates of A.
X
ψ= cm ψm , Aψm = λm ψm ,
m

where the cm ’s are complex numbers. And we claim that

Prob(A = λm ) = |cm |2 .

Proof: X
hAi = hψ|A|ψi = cn c∗m hψm |A|ψn i.
n,m
∗
But since A is hermitian, A = A acting on the bra gives

hψm |A|ψn i = λm hψm |ψn i,

and A acting on the ket gives

hψm |A|ψn i = λn hψm |ψn i.
So if λm 6= λn , then hψm |ψn i = 0. We assume that all eigenvalues are distinct. Later we’ll discuss that we
can always choose the bases for the vector spaces such that the distinct eigenvectors are orthogonal. And we can
normalise them by the condition that each one of them has norm one, i.e., hψn |ψn i = 1.

So we assume that m = n. Hence, X

hAi = |cn |2 λn .
n
P
But we know from basic probability that hAi = n P (A = λn )λn . Hence,

P (A = λn ) = |cn |2 . 

This is Bohr’s probabilistic interpretation. Now, take ψ as the state we are in, and represent a particular state
with ψm . Then
|cm |2 = | hψm |ψi |2 .
P
Proof: Let ψ = n cn ψn . Then
X
hψm |ψi = hψm |cn ψn i = cm hψm |ψm i = cm . 
n

This is called the overlap of ψ with ψm . The important point here is that if we measure the state ψ and find it
to be ψm , then it’s no longer ψ. So the wavefunction abruptly jumps, or, collapses because of a measurement!

2 Radially Symmetric Problems

The universe is spherically symmetric; many interesting problems in physics have spherically symmetry.

17
2.1 The Hydrogen Atom

Take the hydrogen atom. Its Hamiltonian is given by

p~2
H= + V (r),
2m
where the potential part depends on the radius only, not the angles. When we talk about “solving problems”, we
mean finding solutions to
∂ψ(~x, t)
Hψ(~x, t) = i~ .
∂t
This can be done in two steps. Firstly, find eigenvectors and eigenvalues of H, i.e.,

Hψi (~x) = Ei ψi (~x).

We only need to consider a time-independent ψ(~x) since for a time-dependent ψ(~x, t), we can always write
X
ψ(~x, t) = ci (t)ψi (~x),
i

so that X X
Hψ(~x, t) = ci (t)Hψi (~x) = ci (t)Ei ψi (~x)
i i

and
∂ψ X ∂ci (t)
i~ = i~ ψi (~x).
∂t i
∂t
Hence,
∂ci (t)
i~ = Ei ci (t),
∂t
and we solve for ci (t) as
ci (t) = ci (0) e−iEi t/~ .
Therefore, X
ψ(~x, t) = ci (0) e−iEi t/~ ψi (~x).
i
P
All we need to know is what the state is like at t = 0, i.e., the initial condition ψ(~x, 0) = i ci (0)ψi (~
x). But we
can simply use the overlap to find
ci (0) = hψi |ψ(t = 0)i .
Hence all time-dependent problems reduce to solving

Hψi (~x) = Ei ψi (~x).

2.2 The Laplacian

Using the Laplacian ∇2 , we write

~2 2
H=− ∇ + V (r).
2m
Our conventions for spherical coordinates are

x = r sin θ cos φ; y = r sin θ sin φ; z = r cos θ,

with 0 < θ < π and 0 < φ < 2π.

18
 The statement of spherical symmetry corresponds to the system’s independence of θ and φ. Our goal now is
to understand what the ∇2 is in spherical coordinates. The angular momentum will be a main player. Recall the
invariant line element

ds2 = dx2 + dy 2 + dz 2
= dr2 + r2 dθ2 + r2 sin2 θdφ2
≡ gij dxi dxj .

Note that g ij is the inverse of gij such that g ij gjk = δki . (Repeated indices are summed over.) In spherical
coordinates,  
1 0 0
gij = 0 r2 0 .
0 0 r sin2 θ
2

Now, the Laplacian is what allows integration by parts such as

Z Z
|∇ψ| d x = − ψ∇2 ψd3 x.
2 3

√ √
Setting g≡ det g, we start by looking at the volume element in

√
Z Z
|∇ψ| dV = |∇ψ|2 g d3 x
2

√
Z
= ∂i ψ∂j ψg ij g d3 x
√ √
Z
1
= − ψ √ ∂i (g ij g∂j ψ) g d3 x.
g

In general coordinates,
1 √
∇2 = √ ∂i (g ij g)∂j .
g
√
Substituting in g = r2 sin θ for the spherical coordinates case, we have
 
1 1
∇2 = 2 ∂r (r2 sin θ)∂r + ∂θ sin θ∂θ + ∂φ ∂φ
r sin θ sin θ
1 1 1
= 2 ∂r r2 ∂r + 2 ∂θ sin θ∂θ + 2 2 ∂φ2
r r sin θ r sin θ
2 1 2
≡ ∇r + 2 ∇θ,φ .
r
Claim:  2
1 1
∂r r2 ∂r = ∂r r .
r2 r

19
Proof: It’s important to remember that we have to act ∂r on everything on the right as well as pass it through to
the very right (to act on some state). We have
       
1 1 1 1 1 1 1 2 1
∂r r ∂r r = ∂r r ∂r + = (∂r (r∂r )) + ∂r r = ∂r2 + ∂r = 2 ∂r r2 ∂r . 
r r r r r r r r r
Further, clearly
 2
1 1 2
∂r r = ∂ r.
r r r
We’ll be using these interchangeably. Let’s now consider the Laplacian in physics terms. How do we think of

p2 = −~2 ∇2

in problems with radial symmetry? Classically,

p~ = pr r̂ + p~⊥ = pr r̂ + r̂ × p~,

which gives
 ~r × p~ 2 2
 
2 2
p = |r̂ · p~| + 
  = p2r + L .
r  r2
We see some similarities between this expression and our expression for ∇2 . It too consists of a radial piece and
an angular piece. Notice first that there is no ordering ambiguity in
~ = ~r × p~
L

because of the nice cross product property (the position vector and the momentum along this particular position
vector never get multiplied together, e.g., Lx = ypz − zpy ). Hence we can use it in quantum mechanics. For the
radial piece, classically,
pr = r̂ · p~.
But the dot product is unlike the cross product: there is ordering ambiguity in terms like xpx . Hence we do
the most sensible thing of defining
1
pr = (r̂ · p~ + p~ · r̂).
2
The first term
1 1 ~r i~ ∂
r̂ · p~ = (−i~∇) = − ,
2 2r 2 ∂r
and the second term
1 1 ~r
p~ · r̂ = (−i~)∇ · ,
2 2 r
where
1 x2 1 y2 1 z2 3 r2
     
~r x y z 2
∇ · = ∂x + ∂y + ∂z = − 3 + − 3 + − 3 = − 3 = .
r r r r r r r r r r r r r
Hence    
1 i~ 2 ~r 1 1
p~ · r̂ = − + ·∇ = −i~ + ∂r .
2 2 r r r 2
Finally, we have the form of pr as a result of the non-commuting nature of ~r · p~,
 
1 1 1
pr = (r̂ · p~ + p~ · r̂) = −i~ + ∂r = −i~ ∂r r.
2 r r

Now we deal with the angular piece, which is crucial to our understanding of angular momentum. Since r2
commutes with L2 (a fact we’ll prove later), we can write
~ ·L
L ~
2
.
r
We have the commutation relations
[Li , Lj ] = i~ijk Lk .

20
 In fact, we claim that for any vector Vj ,

[Li , Vj ] = i~ijk Vk ,

i.e., L is a generator of rotation of V . For example,

[Li , xj ] = i~ijk xk .

Proof: Writing Li compactly as

Li = ijk xj pk = −i~ijk xj ∂k ,
we have
[Li , xl ] = −i~ijk [xj ∂k , xl ] = −i~ijk xj δlk = −i~ijl xj = i~ilj xj . 
Another example is
[Li , pj ] = i~ijk pk .
Proof:
[Li , pl ] = (−i~)2 ijk [xj ∂k , ∂l ] = (−i~)2 ijk (−δjl ∂k ) = i~ilk (−i~∂k ) = i~ilk pk . 
Theorem: If two commuting vector operators Vi and Wj transform as vectors according to

[Li , Vj ] = i~ijk Vk , [Li , Wj ] = i~ijk Wk .

then their cross product also transforms as a vector.

Proof: We have
~ ×W
(V ~ )i = ijk Vj Wk .

Hence,
~ ×W
[Li , (V ~ )l ] = ljk [Li , Vj Wk ]
= ljk ([Li , Vj ]Wk + Vj [Li , Wk ])
= i~ljk (ijm Vm Wk + Vj ikm Wm )
= i~[(
δli  − δ δ )V W + (δ δ − δ 
δkm lm ki m k lm ji li δjm
)Vj Wm ]
= i~(−Vl Wi + Vi Wl )
~ ×W
= i~ilk (V ~ )k . 

~ = ~r × p~ satisfies [Li , Lj ] = i~ijk Lk . So does L

Indeed, this theorem implies that L ~ commute with scalars?

[Li , Vj Vj ] = [Li , Vj ]Vj + Vj [Li , Vj ] = i~ijk {Vk , Vj } = 0,

since ijk is antisymmetric under the exchange of j and k but the anti-commutator {Vk , Vj } is obviously symmetric
under the exchange of these indices. Hence we have relations such as

[Li , r2 ] = 0, [Li , L2 ] = 0.

Let’s now return to the Hamiltonian

p2
H= + V (r).
2m
Since H consists of scalars only, we have
[Li , H] = 0.
This is equivalent to the statement of rotational symmetry. So we also have

[H, L2 ] = 0.

Notice that Li cannot contain a ∂r term so [Li , r] = 0. We now want to establish

L2 ~2
−~2 ∇2 = − ∂r r2 ∂r .
r2 r2

21
Proof:

L2 ~2
2
= − 2 ijk ilm xj ∂k xl ∂m
r r
~2
= − 2 (δjl δkm − δjm δkl )xj ∂k xl ∂m
r
~2
= − 2 (xj ∂k xj ∂k − xj ∂k xk ∂j )
r
~2 2 2
= − 2 (r ∇ + xj ∂j − 3xj ∂j − xj xk ∂j ∂k )
r
~2 2 2
= − 2 (r ∇ − 2r∂r − r2 ∂r2 )
r  
1
= −~2 ∇2 − 2 ∂r r2 ∂r . 
r

2.3 L2 and Lz

Now, suppose we have operators Ai and Aj . If

[Ai , Aj ] = 0,

then there can be a function ψ which is the eigenfunction of both of the operators simultaneously. Suppose

[Ai , Aj ] 6= 0,

then,
Ai Aj ψ = Ai (aj ψ) = aj ai ψ = ai aj ψ,
but
Aj Ai ψ = Aj (ai ψ) = ai aj ψ
as well. Hence we require [Ai , Aj ] = 0. Given this, our [H, L2 ] = 0 gives

L2 ψ = αψ.

Then analogously, does [H, Li ] = 0 give Li ψ = βψ? No, since the Li ’s don’t commute among themselves. We
can however pick a direction and take
Lz ψ = βψ.
Let’s now substitute α for L2 . Our Hamiltonian becomes
" 2 #
~2 1 d

α
− r + + V (r) ψ = Eψ.
2m r dr 2mr2

Notice that this eigenvalue problem only fixes the radial part. Let’s now explore the reason why the eigenstates
of the Li ’s fix the angular part. We have Lz = xpy − ypx = −i~(x∂y − y∂x ).

Claim:
Lz = −i~∂φ .
Proof:

∂φ = (∂φ x)∂x + (∂φ y)∂y + (∂φ z)∂z

= −r sin θ sin φ∂x + r sin θ cos φ∂y
= −y∂x + x∂y . 

Hence [H, Lz ] = 0 implies that

H(−i~∂φ )ψ = −i~∂φ (Hψ),

22
i.e.,
∂φ H = 0.
We also have
Lx ψ = i~(sin φ ∂θ + cot θ cos φ ∂φ )ψ;
Ly ψ = i~(− cos φ ∂θ + cot θ sin φ ∂φ )ψ.
Notice that there is no r−dependence at all. We can check that these are correct by choosing, for example,
φ = π/2 to get Lx ψ = i~∂θ ψ. As we can see, in the coordinates we choose, Lx and Ly are much messier than Lz
to work with.

We’ll now proceed to find values of α and β in a quick way. We can take V to be anything that’s not singular.
Here, wlog, take it to be 0. Then
~2 1 d2
   
α
− r + ψ = Eψ.
2m r dr2 2mr2
E is not singular, therefore there is no reason for the wavefunction to be singular at the origin either. We can
take ψ = rl so the RHS goes like rl . But then the LHS goes like rl−2 , so they have to cancel. We have

~2 1 d2 l+1 α l−2
− 2
r + r = Erl ,
2m r dr 2m
or,
~2
 
α
− (l + 1)l + rl−2 = Erl .
2m 2m
This immediately implies the eigenvalues

α = ~2 l(l + 1), l ∈ Z≥0 .

l has to be a non-negative integer since if we do a power series expansion of a function to some power, having
negative numbers or fractions as the power will give terms in the series which blow up at the origin, i.e., we’ll
encounter singularities which render inconsistency.

Recall that in the probabilistic interpretation, the probability of finding a particle goes like the square of the
wavefunction, i.e., r2l . This means that near the origin, there is a very high vanishing power if l is large, i.e., there
is a smaller and smaller probability of finding the particle at the origin at large angular momenta.

Next, we tackle
−i~∂φ ψ = βψ.
We can easily write down the general solution

ψ = eimφ f (r, θ), β = m~, m ∈ Z.

m has to be an integer since the wavefunction is single-valued. Since L2 = L2x + L2y + L2z , we also have β 2 ≤ α.
Hence,
β 2 = m2 ~2 ≤ ~2 l(l + 1),
or,
m2 ≤ l(l + 1), |m| ≤ l.
So because of the periodicity of the wavefunction, the angular quantum numbers are quantised.

23
2.4 Spherical Harmonics Ylm (θ, φ)

Let’s now consider a unit sphere, representing ψ(θ, φ). Is there any way to think about arbitrary functions on
the sphere other than using θ and φ? Yes, we can always have

rl f (θ, φ) = xi y j z k ,

i.e., some monomial subject to the condition x2 + y 2 + z 2 = 1. But each x, y, z gives an r if we consider their form
in spherical coordinates. Hence i + j + k = l, i.e., the degree of the monomial is l.

Degree (l) Polynomial m

0 1 0
1 x, y, z ±1, 0
2 x2 , y 2 , z 2 , xy, xz, yz (but with constraint x2 + y 2 + z 2 = 1) ±2, ±1, 0

We can set
x± ≡ x ± iy = r e±iφ sin θ.
Now let’s do the counting. The monomials are basically the integer points inside this triangle.

This gives 21 (l + 2)(l + 1) terms. But x2 + y 2 + z 2 = 1 tells us that if we are able to go two degrees lower, we’re
including something that we should not have included. Hence we have, for a given l, the degeneracy
1 1
(l + 2)(l + 1) − l(l − 1) = 2l + 1.
2 2
Notice that if we write
n n
x++ x−− ,
then m = n+ − n− .

Let’s write down some of the famous spherical harmonics, the Ylm (θ, φ)’s. We normalise them such that when
integrated over the angular piece, Z
|Ylm (θ, φ)|2 sin θ dθdφ = 1.

• l = 0:
1
√ .
4π
• l = 1:
- m = 1: r
3
− sin θ eiφ ;
8π

24
 - m = 0: r
3
cos θ;
4π
- m = −1: r
3
sin θ eiφ .
8π
Now, notice that
∇2 : deg(l) → deg(l − 2).

But recall the cancellation of the rl−2 terms in the radial part of the Schrödinger equation above. Hence,
∇2 rl Ylm (θ, φ) = 0.

And we have
X
∂x2 + ∂y2 + ∂z2 αijk xi y j z k = 0.

Take ax2 + by 2 + cz 2 . Then a + b + c = 0 since

∇2 (ax2 + by 2 + cz 2 ) = 0.

• l = 2:
- m = 2: r r
15 2 15
x = sin2 θ e2iφ ;
32π + 32π
- m = 1: r r
15 15
− x+ z = − sin θ cos θ eiφ .
8π 8π
- m = 0: r r
5 5
(x+ x− − 2z 2 ) = (3 cos2 θ − 1).
16π 16π
- m = −1: r r
15 15
x− z = sin θ cos θ e−iφ .
8π 8π
- m = −2: r r
15 2 15
x = sin2 θ e−2iφ .
32π − 32π
Let’s write
Ylm (θ, φ) = eimφ Plm (θ),
where the Plm (θ)’s are the Legendre polynomials. Now using the angular part of the Laplacian, we get
1 d dP m m2 m
− sin θ l + Pl = l(l + 1)Plm .
sin θ dθ dθ sin2 θ
Now, under parity transformation,
θ → π − θ, φ → φ + π.
Hence,
Ylm (π − θ, φ + π) = (−)l Ylm (θ, φ).
Also note that Z
0
(Ylm )∗ Ylm
0 dΩ = δl,l0 δm,m0 .

In summary, we see that there is a one-to-one correspondence between the Ylm (θ, φ)’s and some monomial f (xi )
in cartesian coordinates subject to the condition i xi = 1 (i.e., that it’s of degree l), satisfying ∇2 f (xi ) = 0.
P 2

25
2.5 The Radial Part R(r)

Let us now tackle the R(r) part in

ψ ≡ R(r)Ylm (θ, φ),
for all spherically symmetric problems. Cancelling the Ylm (θ, φ)’s from both sides, we have
" 2 #
~2 1 d ~2 l(l + 1)

− r + + V (r) R(r) = ER(r).
2m r dr 2mr2

Define
u(r)
R(r) ≡ .
r
Then we have
~2 d2
 
− + Veff (r) u(r) = Eu(r),
2m dr2
where
~2 l(l + 1)
Veff (r) = + V (r).
2mr2
This is like a one-dimensional problem. There are a few things to note here. Firstly, r ≥ 0. Secondly, u(r) ∼ rl+1
as r → 0. Also recall our normalisation condition
Z Z
|ψ|2 r2 dΩdr = |RYlm |2 r2 dΩdr = 1.

We had Z
|Ylm |2 dΩ = 1.

Hence, Z ∞ Z ∞
|u|2 dr = r2 |R|2 dr = 1.
0 0

We’ll specialise to solve the hydrogen atom problem from this point onwards.

This problem looks radically different for the l = 0 and the l 6= 0 cases, since l = 0 gives α = 0 and we simply
have the V (r) < 0 curve as our effective potential. Can we have infinitely negative energy? Classically, yes, but
the quantum theory is smarter. Let’s solve our problem, looking at the E < 0 bound state for now.

d2 l(l + 1) 2mZe2
 
− 2+ − u(r) = −κ2 u(r),
dr r2 ~2 r
where r
2mE
κ≡ − ,
~2

26
i.e.,
~2 k 2
E=− .
2m
Let ρ ≡ κr. In terms of this dimensionless quantity, we have

d2
 
l(l + 1) 1
− 2+ − ξ u(ρ) = −u(ρ),
dρ ρ2 ρ
where
2mZe2
ξ≡ .
κ~2
We have the conditions that as ρ → 0,
u ∼ ρl+1 ,
and as ρ → ∞,
d2 u
∼ u,
dρ2
which gives
u ∼ A e−ρ ,
where the eρ term vanishes since u must be normalisable. So in general,

u(ρ) ∼ ρl+1 e−ρ F (ρ).

We have the conditions that F (0) ∝ 1, and that F (∞) cannot grow too fast. In fact,

u(ρ) ∼ ρl+1 e−ρ

is a solution! But let’s find something more general by substituting u(ρ) ∼ ρl+1 e−ρ F (ρ) back into the Schrödinger
equation above. This gives  
00 l+1 ξ − 2(l + 1)
F −2 1− F0 + F = 0.
ρ ρ
At ρ = 0, since F (0) ∝ 1 we have ξ = 2(l + 1). Let’s now use the usual power series method to find recursion
relations, i.e., we write
X∞
F (ρ) = ak ρk , 6 0.
a0 =
k=0

This gives
ak+1 −ξ + 2(l + 1 + k)
= .
ak (k + 1)(k + 2(l + 1))
So for large k,
2
ak+1 ∼ ak .
k
Hence
2k
ak ∼ ,
k!
and we have
∞
X (2ρ)k
F (ρ) ∼ = e2ρ ,
k!
k=0

but this is a non-renormalisable solution! We need some fine-tuning here. A fallacious assumption we made was
that ak 6= 0 for any k. The only way for it to be 0 such that we don’t get an exponentially growing solution is for
the numerator to vanish at some stage. Let n ≡ l + 1 + k > l, then we require

ξ = 2n.

F (ρ) is a polynomial of degree k = n − l − 1. These are the Laguerre polynomials,

F (ρ) = L2l+1
n−l−1 (2ρ).

27
 Recall our expressions relating ξ, κ and E. Substituting ξ = 2n, we have
1
κ= ,
na
where the Bohr radius
~2 0.5 × 10−8
a= = cm.
mZe2 Z
And we have
m2 Z 2 e4 1 13.6Z 2
E=− 2 2
=− eV.
2~ n n2
Putting everything together, we have found that
l −κn r
ψ(r, θ, φ) = Ylm (θ, φ)L2l+1
n−l−1 (2κn r) × (κn r) e ,

where for a given l, m ranges from −l to l, and n = l + 1, l + 2, .... The wavefunction is normalised such that
Z
|ψ|2 r2 dΩ = 1.

So for a given energy level, how many states have that energy? For any n, we have n2 being the degeneracy
due to the possible values of (l, ml ) that we can choose. In fact, the degenerative states will all split. We’ll come
back to this when we discuss spins, and later, the Runge-Lenz symmetry.

2.6 Decay Rates

Now, let’s compute the decay rates. The technology we have is still insufficient, but we can have the formula
first and get back to it when we talk about perturbative theory. The classical formula for power,
¨|
2 e2 |~x dE
P = 3
= .
3 c dt
When going from an initial to a final state,

Ei − Ef = ~ω.

And the decay rate

1 2ω 3 e2
Γ= P = |~xif |2 ,
~ω 3c3 ~
where
|~xif |2 = | hf |~x|ii |2 + | hi|~x|f i |2 ,
and a “real” derivation involving Einstein’s A and B coefficients will give us

4ω 3 e2
| hf |x|ii |2 + | hf |y|ii |2 + | hf |z|ii |2 .


Γ= 3
3c ~
This already gives us some selection rules. Firstly, ni > nf , otherwise decay cannot happen. What are the
possible initial and final l’s? The formula tells us that x acting on |ii gives |f i, so we claim that ∆l = ±1, and
∆m = 0, ±1. Recall the states’ representation as monomials of degree l. If we multiply them by x, we are one
degree higher. But remember our constraint relating them with the two-degree lower states. Hence the ∆l = ±1.
Now, recall that m comes from ∼ e±imφ . z has no φ dependence, and x ± iy ∝ e±imφ . Hence ∆m = 0, ±1. We’ll
tackle the selection rules in detail later.

28
2.7 The Two-Body Problem

Up till now, we’ve been using the mass of the electron in the hydrogen atom problems. Let the nucleus have
mass m1 , and the electron m2 , then the problem has two degrees of freedom. Then, the centre of mass position
and momentum
m1 ~x1 + m2 ~x2
~xcm = , p~cm = p~1 + p~2 ,
m1 + m2
and the relative position
~xrel = ~x1 − ~x2 .
Is the relative momentum
p~rel = p~1 − p~2 ?
Not really. In quantum mechanics, p~ is defined through its dependence on ~x, i.e., ~x in p~ = −i~∇ should be ~xrel .
We want
[~xcm , p~cm ] = i~, [~xrel , p~rel ] = i~;
[~xrel , p~cm ] = 0 = [~xcm , p~rel ].
So we can take  
p~1 p~2 m1 m2
p~rel = µ − , µ= .
m1 m2 m1 + m2
The Hamiltonian
p~21 p~2
+ 2 + V (|~r1 − ~r2 |) ≡ Hcm + Hrel ,
2m1 2m2
where
p~2cm p~2rel
Hcm = , Hrel = + V (~rrel ).
2(m1 + m2 ) 2µ
And the wavefunction
ψ(~x1 , ~x2 ) ≡ ψ1 (~xcm )ψ2 (~xrel ),
where
~
ψ1 (~xcm ) = eikcm ·~xcm ,
and ψ2 (~xrel ) is the ψ(~r) that we had been computing. The total energy

p~2cm
E= + Erel , p~cm = ~~kcm ,
2(m1 + m2 )
2
where Erel is our good old −13.6 Zn2 eV.

2.8 Three-Dimensional Harmonic Oscillator

The harmonic oscillator sets the stage for us to tackle quantum mechanics. Assuming spherical symmetry so
that the x acts as our r in earlier problems,

p~2 1 p~2 1
H= + kx2 ≡ + mω 2 x2 .
2m 2 2m 2
It is still solvable using the Ylm ’s and the radial equation, but it turns out that there’s something simpler that
we can do. First separate the three-dimensional problem into three one-dimensional problems, writing

ψ(x1 , x2 , x3 ) ≡ ψ1 (x1 )ψ2 (x2 )ψ3 (x2 ).

Then Hψ = Eψ gives

H1 ψ1 (x1 )ψ2 (x2 )ψ3 (x2 ) + ψ1 (x1 )H2 ψ2 (x2 )ψ3 (x2 ) + ψ1 (x1 )ψ2 (x2 )H3 ψ3 (x2 ) = (E1 + E2 + E3 )ψ1 ψ2 ψ3 .

29
 ~2
p
Now, 2m + 21 mω 2 x2 motivates us to think of

|p + ix|2 = (p + ix)(p − ix).

Define
1 1
a≡ √ (p − imωx), a† ≡ √ (p + imωx).
2m~ω 2m~ω
Classically, i.e., without taking non-vanishing commutators into consideration,
 2 
† 1 p 1 2 2
a a= + mω x .
~ω 2m 2

Note that a† a is dimensionless.

Claim:  
1
H = ~ω a† a + .
2
Proof:
p2 1 1  1
RHS = + mω 2 x2 + ω[x,
 p] + ~ω = H. 
2m 2 2
 2
It’s easy to find that
[a, a† ] = 1;
[H, a† ] = ~ωa† , [H, a] = −~ωa.
Hence,
[H, a]† = −[H, a† ].
Given an eigenstate of H, called |αi, then

H(a† |αi) = [H, a† ]|αi + Ea† |αi = (E + ~ω)a† |αi,

and
H(a|αi) = [H, α]|ai + Ea|αi = (E − ~ω)a|αi.
†
Hence a |αi and a|αi are eigenstates of H too, with eigenvalues E + ~ω and E − ~ω, shifting E up and down
by ~ω, respectively. That’s why a† and a are referred to as creation and annihilation operators.

Can we have energy being raised and lowered indefinitely? Infinite negative energy is impossible since

a|αi2 = hα|a† a|αi ≥ 0

 

gives
 1 1
hα|H|αi = E = ~ω α|a† a|α + ~ω hα|αi ≥ ~ω.

2 2
The problem can be solved if we reach a zero state at some point. We can set

a|αi ≡ 0,

such that  
1 1
H|αi = ~ω a† a + |αi = ~ω.
2 2
To find the ground state ψ, take

! 1
0 = aψ = √ (−i~∂x − imωx)ψ,
2mω~
which gives us
mωx2
 
ψ = C exp − .
2~

30
 p
Notice that ψ is a Gaussian with width ~/mω. To find C, simply normalise the state according to
Z ∞
|ψ|2 dx = 1.
−∞

And we have  mω  14
C= .
~π
The ground state is unique, and we’ll denote it with |0i from now on. So we have
1
H|0i = ~ω|0i.
2
Now let’s go up. We have
3
Ha† |0i = ~ωa† |0i.
2
But can a† |0i = 0 as well? No, since

a(a† |0i) = ([a, a† ] + a† a)|0i = |0i.

Since a acting on a† |0i is non-trivial, a† |0i cannot be zero. And in turn, all the higher states obtained through
†
a are non-trivial. Moreover, we can always come back to the same lower state using a. Let’s define

|ni ≡ c(a† )n |0i.

Then  
1
H|ni = n + ~ω|ni.
2
Claim:
a|ni ∝ |n − 1i.
Proof: We can commute the a to the very right, passing through the a† ’s using [a, a† ] = 1 continuously. This gives

a(a† )n |0i = a† aa† · · · a† |0i + a† · · · a† |0i = · · · = n(a† )n−1 |0i. 

The ground state is normalised such that

h0|0i = 1.
We want to demand  !
hn|ni = |c|2 0|an (a† )n |0 = 1.

We have
0|an (a† )n |0 = n 0|an−1 (a† )n−1 |0 = · · · = n! h0|0i .




Hence,
1
|ni = √ (a† )n |0i.
n!
2
Now, we know that |0i is of the form e−αx . Then using our definition of a† in terms of operators x and p, we
have 2
a† |0i = bx e−αx ,
2
(a† )2 |0i = (b0 x2 + b00 ) e−αx ,
etc. In fact, we have
2
|ni = Pn (x) e−αx ,
where Pn (x) are the Hermite polynomials. They have the property that the parity of n is the same as the parity
of Pn (x), i.e.,
Pn (−x) = (−)n Pn (x).
Claim: √
a† |ni = n + 1|n + 1i.

31
Proof:
(a† )n+1 √ (a† )n+1 √
 
† 1
a √ (a† )n |0i = √ |0i = n + 1 p |0i = n + 1|n + 1i. 
n! n! (n + 1)!
Similarly, √
a|ni = n|n − 1i.
Now we briefly discuss a powerful theorem, called Wick’s theorem. Firstly, notice that since a + a† ∝ p and
a − a† ∝ x, any number of x’s and p’s sandwiched between states |ni and |mi can be put into the form

0| · · · (a† )m |0 .



If the number of a’s and the number of a† ’s sandwiched between the |0i’s don’t match, then the whole expression
vanishes. Otherwise, we can use Wick’s theorem to do fast computations. For example, given a state

0|aa† aaa† a† |0 ,



we can contract pairs of left a’s and right a† ’s according to

h0|aa† aaa† a† |0i,

or,
h0|aa† aaa† a† |0i.
Hence,
0|aa† aaa† a† |0 = 2.



Let’s come back to our oscillator problem.

   
3 3
H = ~ω a† 1 a1 + a† 2 a2 + a† 3 a3 + = ~ω n1 + n2 + n3 + ,
2 2

where we call n ≡ a† a the number operator.

Now, we should be able to rewrite everything in terms of spherical harmonics, since we are dealing with a
spherically symmetric problem.

[ht]

State (l) Number of Ways l

|000i 1 0
|100i 3 1
|200i and |110i 3+3=6 2 and 0

3 Principles of Quantum Mechanics

32
3.1 Preliminaries

Quantum mechanics postulates that physical states can be represented as vectors in the Hilbert space, so
operations on Hilbert spaces will be a focus of our discussion. But there are a few things that we have to get
aquatinted with before we get there. Let’s begin with the concept of vector space. Take

~ ∈ V.
~v , w

Then for a ∈ C, we have operations

~ ∈ V,
~v + w a~v ∈ V.
Of course, we can take
~v = ax~ex + ay ~ey + az ~ez = (ax , ay , az ),
and likewise for w,
~ such that
X X X X X
~v + w
~= ai~ei + bj ~ej = (ai + bi )~ei ; c~v = c (ai~ei ) = (cai )~ei .
i j i i i

But we aren’t satisfied with this kind of description. The reason is that choosing some specific vectors ~ei isn’t a
convenient thing to do in quantum mechanics. We want to think about vectors more abstractly, without reference
to specific bases. Different experiments use different ~ei ’s so we want to be more general.

We’ll omit the arrows on vectors from now on. The collection of vectors

{v1 , ..., vr }

are linearly independent if

r
X
ai vi = 0 ⇔ ai = 0 ∀i.
i=1

V is said to be n−dimensional if the maximum dimension of linearly independent vectors is n. If there isn’t
such an n, we call the vector space infinite-dimensional. For now, we will assume a finite n. An n−dimensional
vector space has a basis
B = {v1 , ..., vn },
where each vi are linearly independent. Existence is obvious by the definition of a basis; regarding uniqueness...

Claim: Once we have chosen such a basis, then for every v ∈ V , we can always write it uniquely as
n
X
v= ai vi , ai ∈ C.
i=1

Proof: Suppose bi 6= ai for some i, then take

n
X
v= ai vi
i=1

along with
n
X
v= bi vi .
i=1

If we subtract the former from the later, then we end up with

ai = bi . 

There are infinitely many bases that we can choose from by simply taking linear combinations of the vi ’s. If we
have {v1 , ..., vn } and {w1 , ..., wn }, then
Xn
vi = aij wj ,
j=1

33
which gives
n
X n
X n
X
v= ai vi = ai aji wj = bj wj ,
i=1 i,j=1 i=1

where aji = Aji , A being an n × n matrix, and

n
X
bj ≡ aji ai .
j=1

So the same vector can be written in different bases. If we take

   
a1 b1
 ..   .. 
v ≡  . , w ≡  . ,
an bn

then notice that even though we are talking about the same vector v, the column vectors are different. The relation
between them is simply
w = Av.
Note that we are talking about any linearly independent vectors. Orthogonality, etc do not need to hold for
these statements to be true.

We next move to inner products. Take v, w ∈ V . The interesting properties of the inner product are

v · w = w · v, v · v ≥ 0 (= 0 iff v = 0).

We’ve been using the dot product notation. Dot products are a special case of inner products. They are
products of vectors in Rn , but we need to deal with complex numbers here, and we want our inner product of
something complex to spit out real numbers. We’ll first use mathematician’s notation h ·, · i for inner products.
Physicists like to use the Dirac notation h · |· i. In order to have

hv, vi ∈ Rn , hv, vi ≥ 0,

we simply need the requirement

∗
hw, vi = hv, wi .
The inner product is bilinear, but we’ll encounter a contradiction if we impose the condition naively. For
example, take
∗
z ∗ ≡ hav, wi = (a hv, wi)∗ = a∗ hw, vi
but also,
∗
z ∗ ≡ hav, wi = hw, avi = a hw, vi .
To overcome the contradiction, define

hav, wi ≡ a∗ hv, wi , hv, awi ≡ a hv, wi .

Then we have bilinearity.

n
X
ha1 v1 + · · · + an vn , b1 w1 + · · · + bn wn i = hvi , wj i .
i,j=1

From this point onwards we use the Dirac notation. Take

hvi |vj i ≡ Bij .

Then
∗
hvj |vi i ≡ Bij = Bji .
We say that B is Hermitian if
B = (B t )∗ ,

34
so Hermitian matrices are what we deal with in discussions of inner products. Not all Hermitian matrices are good
enough however. We also need some positivity. :) Now let’s compute
X X X X
hv|wi = h ai vi | bj vj i = a∗i bj hvi |vj i = a∗i Bij bj ∈ C.
i j i,j i,j

So we can take  
a1
 .. 
a∗1 · · · a∗n ,


hv| |vi  . .
an
We now define the notion of an orthonormal basis. It has the nice property that

hvi |vj i = δij ,

i.e., when taking inner products, the matrix B in

 
a1
hv|vi = a∗1 · · · a∗n B  ... 

 

an

is noting but the identity. So how do we choose an orthonormal basis? Start with any basis {v1 , ...vn }. If hv1 |v1 i =
6 1,
then we can take
|v1 i
|w1 i ≡ p .
hv1 |v1 i
This gives us
hw1 |w1 i = 1.
Is the condition hv2 |w1 i = 0 satisfied? In general, no. We try to use |v2 i, but not the component along the |w1 i
direction. So we take
|w2 i ≡ |v2 i − hw1 |v2 i |w1 i,
which gives
hw1 |w2 i = 0.
And normalisation is simple: just divide by the norm of the vector we are normalising. Now, we proceed by
induction. For any |wr+1 i, take
r
X
|wr+1 i ≡ |vr+1 i − hwj |vr+1 i |wj i.
j=1

This way we obtain an orthonormal basis {w1 , ...wn }. We will be choosing orthonormal bases for most of our
applications from now on.

Taking an orthogonal basis {v1 , ...vn }, we can write any vector

X
|wi ≡ aj |vj i,
j

which gives X
hvi |wi = aj hvi |vj i = ai .
j

Hence,
n
X n
X
|vi = hvi |vi |vi i = |vi i hvi |vi ,
i=1 i=1

35
where we call |vi ihvi | the identity transformation. Now, |vi i represents a column vector with all entries 0 except
the ith row, and hvi | represents a row vector with all entries 0 except the ith column. Then, clearly
 
  0
1 1
0
 
 ..  1 0 · · · 0 + 0 0 1 0 · · · 0 + · · · = 1 =

X
|vj ihvj |.
   
.  .. 
. j
0
0

We now move to the discussion of the Schwartz inequality. For real vectors, starting with

v · w = |v||w| cos θ,

since | cos θ| ≤ 1, we have

|v · w|2 ≤ |v|2 |w|2 .
We want a complex vector version of this, i.e., we want to show that

| hv|wi |2 ≤ hv|vi hw|wi .

Proof: Take
hv|wi |vi
|w0 i ≡ |wi − .
hv|vi
Then   
hw|vihv| hv|wi |vi hw|vi hw|vi  hv|vi

0 ≤ hw0 |w0 i = hw| − |wi − = hw|wi − 2 + .
hv|vi hv|vi hv|vi hv|vi 
hv|vi

Hence,
hv|wi hw|vi ≤ hv|vi hw|wi . 
Finally, we can discuss the Hilbert space H, which is a vector space over C with this inner product. Our main
operation on H is linear transformation T such that

T : H → H,

T (av + bw) = aT (v) + bT (w).

In fact, given an orthonormal basis {v1 , ...vn }, then
n
X
T (vi ) = aij vj ,
j=1

or in Dirac notation,
n
X
T |vi i = aik |vk i.
k=1

So we have
hvj |T |vi i = aji ,
and X X X
T |vi = ai T |vi i = ai aji |vj i ≡ bj |vj i ≡ |wi.
i i,j j

Therefore, if V and W have some bases, then every linear map from V to W can be represented by a matrix.
In this context, we see that the identity transformation
X
1= |vi ihvi |
i

is a linear transformation, corresponding to the identity matrix.

36
 Next, we define the adjoint operator, which is a linear transformation. Define

w|T † |v ≡ hv|T |wi.



Indeed, the inner product alone defines the adjoint operation. So we have

vi |T † |vj = (T † )ij = hvj |T |vi i = Tji

∗


.

Hence,
T † = (T t )∗ .
Since the operations of transposition and complex conjugation commute, we have

(T † )† = (((T t )∗ )t )∗ = 1.

Products in linear transformations are straightforward.

n
X n
X n
X
(T1 T2 )ij = hvi |T1 T2 |vj i = hvi |T1 |vk ihvk |T2 |vj i = (T1 )ik (T2 )kj = (T2t )jk (T1t )ki = (T2t T1t )ji .
k=1 k=1 k=1

So we also have
(T1 T2 )† = T2† T1† .
Next, we move to the self-adjoint (Hermitian) operators, defined by

T † = T,

or,
Tij∗ = Tji .
So diagonal entries are real, off-diagonal opposites are complex conjugates of each other.

Now, a transformation T is called diagonalisable iff there exists a basis such that T is diagonal, with its
eigenvalues being the diagonal entries. Also, if T is diagonalisable, then there exists a basis {|ei i} of eigenvectors
|ei i such that
T |ei i = λi |ei i, i = 1, ..., n.
The Hermitian operator is always diagonalisable, and in physics, we almost always deal with transformations
which are diagonalisable, although not all matrices are diagonalisable.

Claim: For any matrices, we can find at least one eigenvector and one eigenvalue such that

T |vi = λ|vi.

Proof: Go to a basis T and take

det(T − λI) ≡ Pn (λ).
Now, if the determinant of a matrix is zero, then the columns forming the matrix are linearly dependent. Then
there is a zero eigenvector. Suppose Pn (λ∗ ) = 0, i.e., det(T − λ∗ I) ≡ det M = 0. Then we have (T − λ∗ I)|vi = 0,
i.e.,
T |vi = λ∗ |vi. 
We now apply this fact to a Hermitian operator T = T † . In an orthonormal basis, we have

T |e1 i = λ|e1 i,

i.e.,     
λ 1 λ
0 ?  0  0 
  ..  =  .. 
    
 ..
.  .  . 
0 0 0

37
 Since T = (T ∗ )t , we see that λ must be real and that the first row, apart from the λ entry, must be zero. What
about the leftover (n − 1) × (n − 1) matrix? Notice that a transformation acting on e2 to en brings back a linear
combination of e2 to en , but nothing from the e1 direction. So we can repeat our first step in the second step,
restricting to the part of the matrix without the first row or column and claiming the existence of one eigenvalue
and eigenvector. So by induction, we can make this matrix completely diagonal. Hence every Hermitian matrix is
diagonalisable, and we have orthonormal basis elements.

Claim: For T Hermitian, given

T |ei i = λi |ei i;
T |ej i = λj |ej i,
if λi 6= λj , then hei |ej i = 0.

Proof:
hei |T |ej i = λj hei |ej i.
Since T † = T and λ is real, we have

hei |T |ej i = hei |T |ej i = λ∗i hej |ei i = λi hei |ej i.

Hence, if λi 6= λj ,
hei |ej i = 0. 
The opposite is not necessarily true. If all eigenvalues are different, then the eigenvectors are unique up to
phases.

Claim: Suppose that for Hermitian matrices A, B, such that

[A, B] = 0.

This is equivalent to saying that there exists a basis in which both are simultaneously diagonalisable.

Proof: Assume that A, B have distinct eigenvalues λ1 , ...λn , α1 , ...αn respectively. If A|ei i = λi |ei i, then

BA|ei i = λi (B|ei i) = A(B|ei i).

But we have showed that the eigenvector corresponding to the eigenvalue λi is unique. Hence B|ei i must be
proportional to |ei i. So |ei i is an eigenvector for B as well. 

Suppose now that not all eigenvalues are distinct, i.e., A can be diagonalised such that

A = diag(λ1 , λ1 , λ2 , λ2 , λ2 , λ3 , · · · ).

This implies that B is block diagonal. Now, restrict B to subspaces since the subspaces do not mix among
themselves. In every subspace, choose a basis such that B is diagonal.

In fact, we can prove by induction that if we have a bunch of Hermitian operators which commute with each
other, i.e., for any pair i, j, we have
[Ai , Aj ] = 0,
then there exists an orthonormal basis such that all the Ai ’s are diagonal.

We can label the basis as

Ak
|λA 1 A2
1 λ2 · · · λk,α i,

representing a simultaneous eigenstate of these operators Ai ’s labelled by their corresponding eigenvalues. Then
if we act, say, A2 on it, we immediately see that we can pick out λ2 . To deal with repeated eigenvalues, i.e., the
leftover degeneracies, add an extra label, say, α. Notice that we can write
X Ak Ak
1= |λA A1
1 · · · λk ihλ1 · · · λk |.
1

{λ}

38
 Now we come to the concept of unitary operators. These linear transformations are the most beautiful part of
quantum mechanics since they realise symmetries. Symmetries must be unitary.

Claim: Unitary operators preserve the inner product hφ|ψi.

Proof: For all |φi, |ψi,

hφ|U † U |ψi = (hφ|U )U ψi = hφ|ψi. 
Now, choose a basis {|ei i}. Then

hei |ej i = hei |U † U |ej i = δij = (U † U )ij .

Hence
U † U = 1.
Claim: A unitary transformation can always be diagonalised; all diagonal elements are phases, i.e., we can put U
into the form
U = diag eiθ1 , · · · , eiθk .

Proof: Recall that every matrix has at least one eigenvector. In other words, there is a basis in which we can write
 
λ
0 ? 
U = . .
 
 .. 
0

Hence, U † U = 1 implies that

|λ| = 1.
Similarly,   
λ α1 ··· αn−1 λ 0 ··· 0
0  α1∗ 
UU† = 1 =  . .
  
..
 ..

?  . ? 
∗
0 αn−1
Hence,
n−1
X
|λ|2 + |αi |2 = 1.
i=1
2
But we have already shown that |λ| = 1. Hence each αi must be zero. We can then restrict to the one-dimension
lower subspace and finish the proof by induction. 

We briefly mention the anti-linear transformation. The most important example is the time reversal operator
T . It takes t 7→ −t in
iEt
ψE (x, t) ∼ e ~ ψn (x).
We can write every unitary matrix
U = exp(iA),
where A is Hermitian. If we take
A = diag(θ1 , · · · , θn ).
Then,
eiA = diag( eiθ1 , · · · , eiθn ).
Can it be written uniquely in this way? No. We can have a family of unitary operators labelled by real number
a, such that
U (a) = eiA(a) , U (0) = 1.
Suppose A(a) = aA, i.e.,
U (a) = eiaA .

39
 Then we say that A generates U . And we have

U (a)U (b) = eiaA eibA = ei(a+b)A = U (a + b).

since A is Hermitian. The punchline is: Hermitian operators generate symmetries.

Now, take
U : H → H.
Through U , for some operators Ti ’s we obtain an equivalence between

hψ|T1 · · · Tn |φi = hψ 0 |T10 · · · Tn0 |φ0 i,

if we define
|φ0 i = U |φi; hψ 0 | = hψ|U † ; Ti0 = U Ti U † ,
since
hψ 0 |T10 · · · Tn0 |φ0 i = hψ|†
U (U T1†
U ) · · · (U Tn†
U )U |φi.
We next discuss the notion of tensor products. In physics, if we want to have more degrees of freedom, we can
tensor product two Hilbert spaces together, combining their degrees of freedom. Take H1 with dimension n1 and
H2 with dimension n2 . Then
H ≡ H1 ⊗ H2
has dimension n1 n2 . Take |vi i ∈ H1 , |wj i ∈ H2 , then

|vi i ⊗ |wj i ≡ |vi wj i ∈ H.

And we have
(a|vi i, |wj i) ∼ (|vi i, a|wj i).
Take T : H1 → H1 such that
T |vi i = aki |vk i.
Then
T |vi wj i = aki |vk wj i.
Note also that
(hu0 | ⊗ hw0 |)(|ui ⊗ |wi) = hu0 |uihw0 |wi.
Using the tensor product, we can construct huge matrices using smaller ones, which is very useful. The nice
properties of matrices are usually inherited as well.

In physics, we often use the notation

T1 ≡ T1 ⊗ 1 : H1 → H1 ;
T2 ≡ 1 ⊗ T2 : H2 → H2 ;
T1 ⊗ T2 ≡ T1 T2 .
So
T1 + T2 ≡ T1 ⊗ 1 + 1 ⊗ T2 .
Now, we can think of discrete situations as a finite-dimensional Hilbert space and a continuous one as an infinite
dimensional Hilbert space. Take
ψ : R → C.
We are interested in the physical states |ψi such that

hψ|ψi < ∞.

How do we approach these in the context of the Hilbert space? We discretise. Say we have a function ψ(x).
Let |xi denote the function which is zero outside of its width  centred at x. We also take its height to be 1 . We
can now write an arbitrary Z
X
|ψi = ψ(xi )|xi i = dx ψ(x)|xi,
i

40
by taking i to infinity and  to 0. Now,
Z x+ 2   1
1
 hx|xi = dx .
x− 2 

Hence,
lim  hx|xi = ∞.
→0

So these are not normalisable, and we have

(
0 0 x 6= x0
hx|x i = .
∞ x = x0

We can write (
0 0 0 x 6= 0
hx|x i = δ(x − x ), δ(x) = .
∞ x=0
Take Z
X
hxi |xi = 1 = dx0 hx0 |xi.
i

Hence, the Dirac-delta function δ(x − x0 ) is such that

Z
dx0 δ(x − x0 ) = 1.

Consider the Gaussian representation

1 x2
δ(x) ≡ δ→0 (x) = √ e− 2 .
 π

Then Z √
π
dx δ(x) = √ = 1.
π
Claim:
ψ(x) = hx|ψi.
Proof: We have Z
|ψi = ψ(x0 )|x0 idx0 .

Then, Z Z
hx|ψi = ψ(x0 )hx|x0 idx0 = ψ(x0 )δ(x − x0 )dx0 = ψ(x). 

In summary,

• Finite-dimensional case: X X
|ψi = ai |ei i; hei |ej i = δij ; δij = 1;
i i
X
hei |ψi = ai ; 1= |ei ihei |.
i

• Infinite-dimensional case:
Z
|ψi = dx ψ(x)|xi; hx0 |xi = δ(x − x0 ); hx|ψi = ψ(x);
Z Z
dx δ(x − x0 ) = 1; 1= dx |xihx|.

41
 One more thing to note is the overlap
Z Z
hφ|φi = hφ|xidxhx|ψi = φ∗ (x)ψ(x)dx.

Below we list some properties of the Dirac-delta function.

R∞
• δ(x) = 0, x 6= 0, −∞
δ(x)dx = 1.
R∞
• −∞ δ(x)f (x) dx = f (0) for a non-zero function f (x).
R∞
• −∞ δ 0 (x)f (x) dx = − δ(x)f 0 (x) dx + δ(x)f (x)|∞ 0
R
−∞ = −f (0), since δ(x 6= 0) = 0.

δ(ax)dx = a1 .
R R
• δ(ax)d(ax) = 1 ⇒
1
R∞
• δ (x) = 2π −∞
dk eikx .
2 2
Proof: Using the regulator e− k /4
, we have
x2
∞ ∞ − 2
Z Z r
dk ikx− 2 k2 dk − 42 (k− 2ix ) − x2 = e 
2 2 4π 1 x2
e 4 = e 2
2
= √ e− 2 = δ (x).
−∞ 2π −∞ 2π 2π  π

Now, in three-dimensions, we simply have

hx0 y 0 z 0 |xyzi = hx0 |xihy 0 |yihz 0 |zi.

So
h~r|~ri = δ(x − x0 )δ(y − y 0 )δ(z − z 0 ) = δ 3 (~r − ~r0 ).
We can also write Z
|ψi = ψ(x, y, z)|xyzi dxdydz,

and in general, Z
|ψi = ψ(~r1 , ~r2 , ...)|x1 y1 z1 x2 y2 z2 · · · xn yn zn i d3 r1 · · · d3 rn .

Note that we are only taking tensor products of the degrees of freedom of spaces.

3.2 Principles of Quantum Mechanics

• For any physical system, we introduce a Hilbert space H. H depends on the system we are interested in.
• The state of a physical system is represented by |ψi ∈ H. It’s normalisable and we take hψ|ψi = 1.
• Physically measurable quantities correspond to Hermitian operators acting on H. The result of measurement
of Ai yields only the eigenvalues of Ai , namely, λi . Moreover,

P (Ai = λi ) = |hλi |ψi|2 .

Now, given |ψ(0)i, what is |ψ(t)i? The time evolution operator is unitary and we have

|ψ(t)i = U (t)|ψ(0)i,

and there is only one unitary operator for all states. A time evolution operator is generated by the Hermitian
operator Hamiltonian. We focus on the time-independent Hamiltonian for now. So we have

U (t) = eiHt/~ .

42
 Hence,
∂ ∂U (t) i i
|ψ(t)i = |ψ(0)i = − HU (t)|ψ(0)i = − H|ψ(t)i.
∂t ∂t ~ ~
And we arrive at
∂
|ψ(t)i = H|ψ(t)i.
i~
∂t
We have been and will be discussing the Schrödinger picture, where states depend on time and operators are
time-independent, as in
hψ(t)|A1 · · · An |ψ(t)i.
There is also the Heisenberg picture, where operators depend on time and states are time-independent, as in

hψ(0)|Â1 (t) · · · Ân (t)|ψ(0)i.

The two pictures are equivalent by the isomorphism between the two Hilbert spaces, since we can go from one
to the other through a unitary operator. As |ψ(t)i = U (t)|ψ(0)i, we also have

|ψ(0)i = U † (t)|ψ(t)i.

Along with
Ân (t) = U † An U,
we have
† † †
hψ(0)|Â1 (t) · · · Ân (t)|ψ(0)i = hψ(t)|U
U A1 U · · · 
U AU 
U |ψ(t)i = hψ(t)|A1 · · · An |ψ(t)i.
In the Hamiltonian formulation of classical physics, we have the Poisson brackets
X  ∂f ∂g ∂g ∂f

{f (x, p), g(x, p)}P B = − ,
i
∂xi ∂pi ∂xi ∂pi

giving us
{x, p}P B = 1.
Quantum mechanically, we have the corresponding commutator relation of

[x, p] = i~.

Now, we can think of translation as a unitary operator. Given x|x0 i = x0 |x0 i, with the unitary translation
operator U (a), we have
x(U (a)|x0 i) = (x0 + a)U (a)|x0 i,
i.e.,
U −1 (a)xU (a)|x0 i = (x0 + a)|x0 i.
Hence, U (0) is the identity operator, and since we are dealing with translation, we require U (a)U (b) ∼ U (a + b),
which gives us
U (a) = e−iaA/~ .
We say that A generators translation, and demand
!
eiaA/~ x e−iaA/~ = x + a

for small a. But if we simply compute, we end up with

ia
eiaA/~ x e−iaA/~ = x + [A, x] + O(a2 ).
~
We therefore demand that
!
[A, x] = −i~.
It is only natural at this point to set A ≡ p since

[x, p] = i~.

43
 d
Hence, the momentum operator p = −i~ dx generates translation, and we take
d
U (a) = eipa/~ = e−a dx .

Note that the reason why we have such pairs as x, p is because one generates the other. We have
X 1  n
†

d
hx|U (a)|ψi = hx|U (a) |ψi = hx − a|ψi = ψ(x − a) = U (a)ψ(x) = −a ψ(x).
n
n! dx

And altogether, we have the commutation relations

[xi , pj ] = i~δij ; [pi , pj ] = 0,

since schematically,
!
U1 (1 )U2 (2 )U1−1 (1 )U2−1 (2 ) ∼ e1 A1 e2 A2 e−1 A1 e−2 A2 = 1 + 1 2 [A1 , A2 ] + O(3 ) = 1.

Next, we can write

hx|p0 i = ψp0 (x).
Along with
p̂|p0 i = p0 |p0 i,
we have
∂ψp0
hx|p̂|p0 i = −i~ = p0 ψp0 (x).
∂x
Then, 0
ψp0 (x) = C eip x/~ .
We want hp|p0 i = δ(p − p0 ), so to find the normalisation constant C, compute
Z ∞ Z ∞
0
dx hp|xihx|p0 i = dx C ∗ C ei(p −p)x/~
−∞ −∞
 0 
p −p
= |C|2 2πδ
~
= 2π|C|2 ~ δ(p0 − p).

Hence,
eipx/~ e−ipx/~
hx|pi = √ , hp|xi = √ ,
2π~ 2π~
and 0 0
∞ ∞
eipx /~ 0 e−ip x/~ 0
Z Z
|pi = dx0 √ |x i; |xi = dp0 √ |p i.
−∞ 2π~ −∞ 2π~
Next, given
hx|Si = ψ(x), hp|Si = φ(p),
how can we related the two?
∞ ∞ 0
e−ip x/~
Z Z
hp|Si = hp|xihx|Si dx = √ ψ(x) dx = φ(p);
−∞ −∞ 2π~
∞ ∞ 0
eip x/~
Z Z
hx|Si = hx|pihp|Si dp = √ φ(p) dp = ψ(x).
−∞ −∞ 2π~
Note also that we can write
3
hx1 x2 x3 |p1 p2 p3 i = hx1 |p1 ihx2 |p2 ihx3 |p3 i = (2π~)− 2 ei~p·~r/~ = h~r|~
pi.

44
 Now we consider the spread ∆ψ A of an observable corresponding to the operator A in a state ψ. With
Ā ≡ hψ|A|ψi, we have

(∆ψ A)2 ≡ hψ|(A − Ā)2 |ψi = hψ|A2 − 2ĀA + Ā2 |ψi = Ā2 − 2ĀĀ + (Ā)2 .

Hence,
(∆ψ A)2 = hψ|A2 |ψi − hψ|A|ψi2 .
We now prove the general statement of the uncertainty principle
1
∆A∆B ≥ |hψ|[A, B]|ψi|,
2
which implies the famous
~
∆x∆p ≥ .
2
Proof: Set
|ψA i ≡ (A − Ā)|ψi;
|ψB i ≡ (B − B̄)|ψi.
The Schwartz inequality tells us that

|hψA |ψB i|2 ≤ hψA |ψA ihψB |ψB i,

where
LHS = |hψ|AB − ĀB̄|ψi|2 ≡ |C|2 ≥ |ImC|2 .
But
hψ|AB − ĀB̄|ψi − hψ|BA − ĀB̄|ψi 1
ImC = = hψ|[A, B]|ψi.
2i 2i
Hence,
1
|hψA |ψB i|2 ≥ |hψ|[A, B]|ψi|2 .
4
But
hψA |ψA i = hψ|(A − Ā)2 |ψi = (∆A)2 .
Hence we arrive at
1
∆A∆B ≥ |hψ|[A, B]|ψi|. 
2
Now, just like how the momentum operator generates spatial translation, the Hamiltonian operator generates
time translations. In this sense, quantum mechanics is ready to made special relativistically invariant. Spatial
translations and time translations are both realised through unitary operators, and since

[H, U ] = 0,

we say that U is a symmetry of our problem. The fact that it’s generated by A implies that

[H, A] = 0.

Claim: [H, A] = 0 is equivalent to saying that A is conserved.

Proof: Take
U (t) = e−iHt/~ .
Then,
∂U i ∂U † i
= − HU ; = U † H.
∂t ~ ∂t ~
So we have Ehrenfest’s theorem
d d 1
hψ(t)|A|ψ(t)i = hψ(0)|U −1 (t)AU (t)|ψ(0)i = hψ(t)|[A, H]|ψ(t)i.
dt dt i~

45
 Hence
[H, A] = 0 ⇔ A is conserved. 
In this case, U (t) only acts on the energy and will not change the eigenvalue of A. So conservation law follows
from commutation with H.

We can also have discrete symmetries. For example, in the Harmonic oscillator case, parity operator

P : x → −x

is a symmetry. The discrete symmetries are also given by unitary operators which preserve norms. Here

U 2 = 1,

and the only possible eigenvalues are α = ±1. So without solving the harmonic oscillator problem, we already
know that the eigenstates are even or odd functions of x.

Now, consider some physical system with Hamiltonian H. What are all the symmetries of the problem? Every
symmetry can be represented by some unitary operator Uα such that

Uα HUα−1 = H.

This is the symmetry statement. The symmetries of a system form a group. Now, the (unitary) realisation or
representation of a group with operation ∗ satisfies

U (g1 )U (g2 ) = U (g1 ∗ g2 );

U (1G ) = I.
-

Aside: Just to be mathematically clear, a representation D(G) of a group G is a linear group action v 7→ D(g)v
on a vector space V , by invertible transformations. D(g) ∈ GL(dim(V )) ∀ g ∈ G, and by linearity,

D(g)(av1 + bv2 ) = aD(g)v1 + bD(g)v2 .

To be a group action D must satisfy

D(g1 g2 ) = D(g1 )D(g2 ).
Also note that
D(1) = 1, D(g −1 ) = D(g)−1 ,
(These are not properties of unitary representations only!)

Another point is that we must choose a basis for V to have explicit matrix representations.

For every group element, we have a representation of it acting on the symmetries of the Hilbert space, i.e., there
is a homomorphism between the two. If U 2 = 1, then there is a basis

U = diag(+1, · · · , +1, −1, · · · , −1).

Now, if g1 ∗ g2 6= g2 ∗ g1 , then
U (g1 )U (g2 ) 6= U (g2 )U (g1 ).
So the corresponding representations of the symmetries in the quantum theory will not be simultaneously
diagonalisable. Then we can choose a basis which is as close to diagonalisation as possible, i.e., we can block
diagonalise.

Next, we have used without proof that

hψ|A|ψi = Ā.

46
Proof: Take X
|ψi = ci |ai i.
i

Then X X X
hψ|A|ψi = (haj |cj )A(ci |ai i) = ci c∗j hai |A|aj i = |cj |2 aj = Ā. 
i,j i,j j

In the context of statistical mechanics, we also have probabilities. And in quantum physics, we can also take
a thermal bath. How do we think about the intrinsic probability of a quantum system together with thermal
probability? For every state |ψi, we introduce an operator

ρψ = |ψihψ|.

Then,
hψ|An · · · A1 |ψi = Tr(|ψihψ|A1 · · · An ) = Tr(ρψ A1 · · · An ).
Note that ρψ is a projection operator since hψ|ψi = 1, giving

ρ2ψ = ρψ .

For any projection operator P , its eigenvalue too satisfies λ2 = λ. Hence we can have the basis

P = diag(1, · · · , 1, 0, · · · , 0).
P
And from i |ei ihei | = 1, we have
X
Pei = 1.
i

If we don’t know which state we are in, but only the statistical probability pα to be in a state, we write
X
ρ= |ψα ipα hψα |.
α

Then we have X
pα hψα |A1 · · · An |ψα i = Tr(ρA1 · · · An ).
α
P
Note that since α pα = 1 and pα ≥ 0, we have

Trρ = 1,

and we can choose the basis

ρ = ρ† = diag(p1 , · · · , pn ).
This is what we call a mixed state of a quantum system. A pure state is one where, for example,

ρ = diag(1, 0, · · · , 0).

In statistical mechanics, using the eigenstates of energy, the density matrix

ρ = |Eα i e−βEα hEα |.

Then,
−βEα
P
α hEα |A|Eα i e
Tr(ρA) = P −βEα
.
α e
How do we translate objects like entropy S in statistical mechanics to quantum mechanics? Suppose we have an
N −dimensional Hilbert space, i.e., we take N of |ei i’s. If we don’t know which state we are in, then what should
ρ be?  
1 1
ρ = diag ,··· ,
N N

47
satisfies Trρ = 1. This is when we have a maximal amount of entropy, since all possible situations are equally likely
here. This system has N configurations, so by definition

S = ln N.

So we can take
S = −Tr(ρ ln ρ)
to be the quantum entropy associated with a state, which is always positive. Note also that for the pure state case,
we have S = 0.

4 Spins

Around 1925, physicists were trying to figure out the spectrum of atoms. The splitting lines showed that there
were more states than expected. So it was suggested that there’s something between l = 0 (which has one state) and
l = 1 (which has three states). They called this extra degree of freedom spin. Spin is basically the representation
of rotation in a quantum system.

The rotation group is given by the transformations

X i → Ri j X j .

In two dimensions for example, we can take

    
x cos θ − sin θ x
= .
y sin θ cos θ y
And the group is abelian in the sense that

R(θ1 )R(θ2 ) = R(θ1 + θ2 ).

It’s not the case in higher dimensions. In three dimensions, we can take
 
cos θ − sin θ 0
Rxy (θ) =  sin θ cos θ 0 .
0 0 1
Then,
[Rxy , Ryz ] 6= 0,
i.e., they are not simultaneously diagonalisable. Rotations R have the property

Rt R = 1.

Notice that
x → Rx, y → Ry.
(Ry)t Rx = y t x.
Let’s expand
R = 1 + iij Tij , Rt = 1 + iij Tij .
Then
Tij = −Tji
t
since R R = 1. So Tij is an antisymmetric matrix. For example, in three dimensions,
 
0 −i 0
T12 =  i 0 0 .
0 0 0

48
 Hence antisymmetric matrices generate rotations. And it has the algebra

[Tij , Tkl ] = −iTil δjk + iTkj δil + iδjl Tik − iδik Tlj .

The number of generators in n dimensions is

1
n(n − 1)
2
since they are anti-symmetric.

Aside: For those who like math, here we give a relevant discussion on Lie groups and Lie algebras.

A Lie group is a group with the structure of a smooth manifold such that group operation G×G → G, (g1 , g2 ) 7→
g1 g2 and inverse G → G, g 7→ g −1 are smooth maps between manifolds.

The Lie algebra g of a Lie group G is the tangent space T1 G to G at the identity element 1 ∈ G. Without
considering the Lie group, we can give the definition that Lie algebra is a vector space g equipped with an anti-
symmetric bilinear operation [ , ] : g × g → g which satisfies the Jacobi identity.

Now, in class we talked about the rotation group in three-dimensions, which is nothing but the Lie group SO(3).
Here, from a more or less mathematical perspective, we discuss SO(3) and its Lie algebra so(3), as well as SU (2)
and su(2), which will soon be useful.

SO(3) = {2×2 real matrices O with OT O = 1, det(O) = 1}.

Let’s consider a curve O(t) = 1 + tX + O(t2 ) ∈ SO(3) with O(0) = 1. OT O = 1 gives
d T
[O O]t=0 = [ȮT O + OT Ȯ]t=0 = ȮT + Ȯ = 0.
dt
det O = 1 gives no extra constraint since all elements in SO(3) near the identity have det = 1. Hence

so(3) = {vector space of 3×3 real antisymmetric matrices}.

Now, let so(3) have bases

     
0 0 0 0 0 1 0 −1 0
T̃1 =  0 0 −1  , T̃2 =  0 0 0 , T̃3 =  1 0 0 .
0 1 0 −1 0 0 0 0 0

Then,
(T̃a )bc = −abc .
Hence,

[T̃a , T̃b ]cd = (T̃a )ec (T̃b )de − (T̃b )ec (T̃a )de
= ace bed − bce aed
= δad δcb − 
δab cd − δbd δca + 
δ δba
δ
cd
= eab edc
= −abe ecd
= abe (T̃e )cd .

Therefore we have the Lie bracket structure

[T̃a , T̃b ] = abc T̃c .

Next,
SU (2) = {2×2 complex matrices U with U † U = I, det(U ) = 1}.

49
 Consider a curve U (t) := 1 + tZ + O(t2 ) ∈ SU (2) with U (0) = 1. U † U = 1 gives

d †
[U U ]t=0 = [U̇ † U + U † U̇ ]t=0 = U̇ † + U̇ = Z † + Z = 0.
dt
Also, in matrix form,  
1 + tZ11 tZ12
U (t) = .
tZ21 1 + tZ22
det U = 1 gives
1 + t(Z11 + Z22 ) + O(t2 ) = 1 + tTr(Z) + O(t2 ) = 1
⇒ Tr(Z) = 0.
Hence
su(2) = {vector space of 3 × 3 complex antihermitian traceless matrices}.
Let su(2) have bases
1
Ta = − iσa
2
where σa are the Pauli matrices, which have the property σa σb = δab I + iabc σc .
1 1
⇒ [Ta , Tb ] = − (σa σb − σb σa ) = − iabc σc = abc Tc .
4 2
Since the Lie bracket structure for su(2) and so(3) are the same, the Lie algebras are isomorphic. In fact, SU (2)
is the universal covering group of SO(3) so their Lie algebras must be isomorphic. The isomorphism is induced by
the universal covering map.

We continue our discussion of the quantum theory. Recall that we had e−iaJ/~ . Since the exponential of J/~
generates unitary transformations, we can take for the representation of rotation in Hilbert space,

Tij 7→ Jij /~,

i.e., Jij /~ should satisfy the same algebra as Tij . In three dimensions,

1
Ji = ijk Jjk .
2
Hence, by the symmetry of rotations,
[Ji , Jj ] = i~Jk .
Explicitly, we can take
     
0 0 0 0 0 i 0 −i 0
J1 =  0 0 −i  , J2 =  0 0 0  , J3 =  i 0 0 .
0 i 0 −i 0 0 0 0 0

Now, for any vector V j ,

[Ji , Vj ] = i~ijk Vk .
We want to represent the rotation of a vector, i.e.,

U −1 (R)Vi U (R) = Rij Vj ,

where U −1 (R) and U (R) are unitary operators and Rij is a number. So we have both

[Ji , Lj ] = i~ijk Lk

and
[Li , Lj ] = i~ijk Lk .

50
 Hence,
[Ji − Li , Li ] = 0.
We define
Si = Ji − Li
to be the extra piece that rotations could include, and call it spin. We have

[Si , Sj ] = [Ji − Li , Jj − Lj ] = i~ijk Sk .

So how do we represent such objects as Li , Si , or Ji , which satisfy such commutation relations, in the Hilbert
space?

Let’s pause for a moment to again consider the hydrogen atom. We are saying that it has the possibility of the
extra piece of spin. Since [S, L] = 0, S has no angular degree of freedom and is independent of the physical space.
So we need to tensor our theory with a new Hilbert space, i.e., H → ⊕α,j Hjα . In other words, since S has new
degrees of freedom, we need to represent it.

Now, recall our maximally commuting

[J 2 , J3 ] = 0.
It’s useful to think in terms of them. Define

J± ≡ J1 ± iJ2 .

Then,
[J3 , J± ] = ±~J± .
Recall that J3 |mi = m~|mi. Hence,

J3 (J+ |mi) = (J3 J+ − J+ J3 + J+ J3 )|mi = ~(m + 1)J+ |mi.

Similarly,
J3 (J− |mi) = ~(m − 1)J− |mi.
Note that if we assume
J 2 |m, αi = ~2 α|m, αi,
where α doesn’t change, then there exists

J+ |mf,α i = 0, J− |mi,α i = 0,

since
hm, α|J 2 |m, αi = ~2 α ≥ m2 ~2 .
In other words, if α is fixed, then m cannot be too big. α is determined by J 2 and J± cannot shift it, since

[J 2 , J± ] = 0.

Next, we have
J12 + J22 = (J1 ± iJ2 )(J1 ∓ iJ2 ) ± i[J1 , J2 ].
Hence, we can write in two ways
J 2 = J± J∓ ∓ ~J3 + J32 .
Hence,
J 2 |mf , αi = ~2 α|mf , αi = (J−
J 2
+ + ~J3 + J3 )|mf , αi,

giving
~2 α = ~2 (mf + m2f ).
Similarly,
J 2 |mi , αi = ~2 α|mf , αi = (J+ 2
− − ~J3 + J3 )|mi , αi,
J

51
giving
~2 α = ~2 (m2i − mi ).
So we have
mi (mi − 1) = mf (mf + 1).
We require that mi < mf , so we take the solution

1
mf = −mi ≡ j, j ∈ Z or Z + ,
2
since mf = mi + k = −mf + k, k ∈ Z gives mf = k/2. Now, there are 2j + 1 states in the ladder. We have
computed that
J 2 = ~2 α = ~2 j(j + 1).
We’ll from now on denote states as
|m, ji, − j ≤ m ≤ j.
So we have
J3 |m, ji = m~|m, ji;
J 2 |m, ji = ~2 j(j + 1)|m, ji.
Notice that if j is an integer (half-integer), then m is also an integer (half-integer). Now, j3 is a generation of
rotation around the z−axis, so if we want to act a rotation of 2π on the state, then write

e2πiJ3 /~ |m, ji = e2πim |m, ji.

So if m is a half-integer, the state only comes back up to a minus sign. This didn’t happen for, say, the hydrogen
atom.

J± |m, ji = C|m ± 1, ji.

Then,
hm, j|J∓ J± |m, ji = |C|2 hm ± 1, j|m ± 1, ji = |C|2
But
J∓ J± = J 2 − J32 ∓ ~J3 .
Hence,
|C|2 = ~2 [j(j + 1) − m(m ± 1)].
The phase of C is fixed such that
p
J± |m, ji = ~ j(j + 1) − m(m ± 1)|m ± 1, ji.

In summary, we have shown that every time we have an algebra of angular momentum, we can find a ladder-like
structure. Of course, a Hilbert space can have ladders of many different sizes. Each of the ladders is called an
irreducible representation (irrep). So we are decomposing our Hilbert space into irreps of the rotation group.

Aside: Let D be a representation of G acting on a vector space V . D is reducible if there exists a proper, invariant
subspace W ⊂ V , i.e., there exists a subspace W such that D(G)W = W . If no such subspace exists, then D is an
irreducible representation.

We briefly discuss the Stern-Gerlach experiment, which originally determined the existence of spins. A beam
of material is passed through a region of strong magnetic fields, and split into two. We have

p2 ~ · B,
~
H= + αS
2m

52
 ~ and B.
where we assume interaction between the S ~ Ehrenfest’s theorem says

dŌ d i
≡ hψ|O|ψi = hψ|[H, O]|ψi
dt dt ~
We have the unsurprising
dx̄ p~
= h i.
dt m
Next,
dp̄i i ~ · B(x),
~ ∂
= αh[S −i~ i ]i,
dt ~ ∂x
i.e.,
d2 x̄i ~ · Si.
~
= −αh∂i B
m
dt2
Suppose the beam is in the z−direction, and the gradient is also in the z−direction. Then we get a beam split
depending on whether S~ is upward or downward. So basically, the spin causes a force which acts on the beam to
split it.

4.1 Addition of Angular Momentum

We refer to expressions like

J~ = S
~ +L
~

as the addition of angular momentum. Let’s now take general

J = J 0 + J 00 .

A general state can be written as 0

,j 00
|j 0 m0 , j 00 , m00 i ⊂ Hj
and the Hilbert space has (2j 0 + 1)(2j 00 + 1) dimensions. Now, it’s easy to count the ladders. If we were given
different ladders with different sizes, we can decide immediately just by looking at the spectrum of j3 ’s what the
possible values of j are. We have
J3 = J30 + J300
such that
J3 |j 0 m0 , j 00 , m00 i = ~(m0 + m00 )|j 0 m0 , j 00 , m00 i.
Let’s check the following cases.
• j 0 = 0, j 00 arbitrary gives j = j 00 ;
• j 0 = 12 , j 00 arbitrary gives j = (j 00 + 21 ) ⊕ (j 00 − 12 );
• general j 0 , j 00 , where j 0 > j 00 gives

j 0 + j 00 j 0 + j 00 − 1 j 0 + j 00 − 2 ··· j 0 − j 00 ··· −j 0 + j 00 ··· −j 0 − j 00

# of states 1 2 3 2j 00 + 1 2j 00 + 1 1

i.e.,
j = j 0 ⊗ j 00 = (j 0 + j 00 ) ⊕ (j 0 + j 00 − 1) ⊕ · · · ⊕ (j 0 − j 00 ) = ⊕|j 0 −j 00 |≤j≤j 0 +j 00 j.

Note that X
dim(LHS) = (2j 0 + 1)(2j 00 + 1) = (2j + 1) = dim(RHS)
|j 0 −j 00 |≤j≤j 0 +j 00

53
 0 00
Expressed in terms of the Clebsch Gordon coefficients C j j ,
X 0 00
|j 0 m0 , j 00 m00 i → |j, mi = C j j (j, m; m0 , m00 )|j 0 , j 00 i.

So for example,
|j = j 0 + j 00 , m = j 0 + j 00 i = |j 0 , j 00 i,
0 00
i.e., C j j
= 1. We now find the next state.

|j 0 + j 00 , j 0 + j 00 − 1i = J− |j 0 + j 00 , j 0 + j 00 i
0 00
= (J− + J− )|j 0 , j 00 i
p p
= ~ j 0 (j 0 + 1) − j 0 (j 0 − 1)|j 0 − 1, j 00 i + ~ j 00 (j 00 + 1) − j 00 (j 00 − 1)|j 0 , j 00 − 1i.

However, in order to normalise, we need to divide the expression by

p
~ (j 0 + j 00 )(j 0 + j 00 + 1) − (j 0 + j 00 − 1)(j 0 + j 00 ).

Next, the Hamiltonian

~ = α [(S
~ ·L
H = αS ~ 2 − S 2 − L2 ] = α [J 2 − J 02 − J 002 ],
~ + L)
2 2
where J 2 , J 02 , J 002 have eigenvalues ~2 j(j + 1), ~2 s(s + 1), ~2 l(l + 1) respectively. Notice that

[J 2 , J 02 ] = [(J 0 + J 00 )2 , J 02 ] = [02
J J 002
+  + 2J 0 · J 00 , J 02 ] = 2[J 0 , J 02 ]J 00 = 0
i

since Ji0 is the generator of rotation around the ith axis, and is a scalar. Hence, we can go from a basis where

J 02 , J 002 , J30 , J300

are diagonal to one where

J 02 , J 002 , J 2 , J3
are diagonal.

We now discuss the Pauli matrices. They are special since the spin of the electron s = 21 . 2S + 1 = 2 so there
are two states. Hence,
S3 = (~/2, −~/2).
Note the notations
| + 1/2i = | ↑i = (1, 0);
| − 1/2i = | ↓i = (0, 1).
Then,  
~ 1 0
S3 = σ3 , σ3 = .
2 0 −1
We have r
1 3 1 −1
S+ | ↓i = ~ − | ↑i = ~| ↑i, S+ | ↑i = 0.
22 2 2
Similarly,
S− | ↑i = ~| ↓i, S− | ↓i = 0.
Recall that
1 1
S1 = (S+ + S− ), S2 = (S+ − S− ).
2 2i
Hence,  
~ 0 1
S1 = σ1 , σ1 = ;
2 1 0
 
~ 0 −i
S2 = σ2 , σ2 = .
2 i 0

54
 Note the properties of the sigma matrices that
σ 2 = 1, σi σj = iijk σk .
Let’s consider rotation around the θ axis.

Claim:
~ θ θ
eiθ·~σ/~ = cos 1 − i sin (σ · θ̂).
2 2
Proof: Suppose θ~ = θẑ. Then
∞ X 1  θ n X 1  θ n
X 1  σ3 n θ θ
eiθσ3 /2 = −iθ = + σ3 = cos 1 − i sin σ3 . 
n=0
n! 2 n even
n! 2i n! 2i 2 2
n odd

Now, every particle that has mass has internal spin S = 0, 1/2, 1, ... Fermions have half integer spin; bosons have
integer spin. An even number of fermions gives bosons, any number of bosons give bosons, and an odd number of
fermions with any number of bosons give fermions. You can have arbitrary spins for the massive particles but...

For massless particles, you cannot take all possible values for S3 . For example, for a spin-1 particle, you can
only have the states of ±1, not 0. This corresponds to the photon, which only has two helicities, ±1, corresponding
to left- or right-handed polarisations: there is no “no-handed” polarisation. Also, the graviton has spin-2 but if we
have a massless particle of spin greater than 2, we won’t have a unitary quantum theory. So the massless case is
very limited.

4.2 Identical Particles

Now, all electrons in the universe are the same. Suppose we have a state of n identical particles, then
|ψin ∈ H1 ⊗ H1 ⊗ · · · ⊗ H1 ,
where H1 denotes the Hilbert space of one particle and we have n copies of it. Let |v1i i be a basis for H1 . Take the
unitary operator Pij such that
α α
Pij |v1α1 · · · viαi · · · vj j · · · vnαn i = |v1α1 · · · vj j · · · viαi · · · vnαn i.
The eigenvalues are ±1. For bosons corresponding to (H1⊗n )symm , Pij = 1 and for fermions corresponding to
(H1⊗n )anti-symm ,
Pij = −1 for all i, j. We list a few k−particle cases below, along with the basis for the Hilbert
space corresponding to the k particles.
• 1 fermion: |v1i1 i, dim = N ;
 
N
• 2 fermions: |v1i1 v2i2 i − |v1i2 v2i1 i, dim = ;
2
• 2 bosons: |v1i1 v2i2 i + |v1i2 v2i1 i, dim = 12 N (N + 1). So we can take the wavefunction
X
ψ(~x1 , ~x2 ) = (ψα (~x1 )ψβ (~x2 ) ± ψα (~x2 )ψβ (~x1 )) .
α,β
 
N
• 3 fermions: Take i, j, k = 1, ..., N , dim = .
3
|α1i i |α2i i |α3i i
 

det |α1j i |α2j i |α3j i = |ijki + |kiji + |jkii − |jiki − |ikji − |kjii (∗).
|α1k i |α2k i |α3k i
So for example, P12 (∗) = −(∗).
The antisymmetric property of fermions corresponds to the Pauli exclusion principle.

55
4.3 Electrons and the Nucleus

We have the Hamiltonian which includes the Coulomb attraction between the electron and the nucleus, as well
as the repulsion between pairs of electrons.
Z  2
Ze2 e2
 X
X pi
H= − + .
i=1
2m |~ri | i<j
|~ri − ~rj |

The repulsion term is hard to deal with, so we don’t consider it for the moment. Then, we have a diagonal
Hamiltonian
Z  2 Z
Ze2
 X
X pi
H= − = Hi .
i=1
2m |~r1 | i=1

Taking
|ψi = |E1,α1 , E2,α2 , · · · , En,αn i,
we see that we get the eigenstates by simply writing H as the individual Hi ’s.
n
X
H|ψi = Ei |ψi.
i=1

For the hydrogen, we can write

|E1 , α1 i = |n1 , l1 , m1 , s = ±1/2i.
Notice that we are dealing with fermions, so the labels must be distinct. Let’s look at some of the lowest energy
states (n = 1). Hydrogen has
|n = 1, l = 0, m = 0, s = ±1/2i
where the first three quantum numbers tell us that we are in the 1s1 states. Helium has

|1, 0, 0, 1/2; 1, 0, 0, −1/2i − |1, 0, 0, −1/2; 1, 0, 0, 1/2i,

which, with normalisation, can be written as

1
√ (| ↑↓i − | ↓↑i).
2

In a two-dimensional Hilbert space, we cannot make a three-part state antisymmetric. So we go to 2s1 , etc.
The Hilbert space is decomposed in terms of the tensor product of the spatial degrees of freedom and the spin
ones. Now, the magic numbers 2, 8, 18, ... come from adding the number of states for each l as follows, where 2
corresponds to the two spin states.
• l = 0: 1 × 2 states;

• l = 1: 3 × 2 states;
• l = 2: 5 × 2 states; etc.
Are there magic numbers associated with the nuclei? Let’s try to look at it in terms of the harmonic oscillator.

• |000is : 1 × 2 states;
• |100ip : 3 × 2 states;
• |200i and |110i: 6 × 2 states; etc.
So the magic numbers here are 2 (He), 8 (16 O), 20 (40 Ca), 40, ... No! In fact, we should get 28 instead of 40. A few
complications arise due to the spin-orbit coupling.

56
4.4 Thermodynamics

  
Ei µN
Pi ∝ exp − − .
kT kT
For bosons,
X 1
ZB = e−nx = ,
n
1 − e−x
and
Ni e−Ni (Ei −µ)/kT
P
1
N̄iB = Pi −N (E −µ)/kT = (E −µ)/kT .
j e j j e i −1
For fermions,
Z F = 1 + e−(Ei −µ)/kT ,
and
e−(Ei −µ)/kT 1
N̄iF = = (E −µ)/kT .
1 + e−(Ej −µ)/kT e i +1
Note that for the Bose-Einstein condensation, we take T = 0, then all bosons are in the same quantum state.
So together they behave like one gigantic particle. Notice that for the fermionic case,
(
F 1, E < µF
N̄i = ,
0, E > µF

where µF is the Fermi energy.

4.5 Crystals

A crystal is an amalgamation of atoms with some periodicity structure. The Hamiltonian commutes with the
translation operator, i.e.,
~ 1 + n2 L
U (n1 L ~ 2 + n3 L
~ 3 )H = HU (n1 L
~ 1 + n2 L
~ 2 + n3 L
~ 3 ).

So we can choose a basis of eigenstates of the Hamiltonian, for which both the Hamiltonian and this operator
are diagonal simultaneously. The H can be very complicated, but if the crystal has exact symmetry under this
translation, the we can use it to analyse the system without solving it. The translation operators should themselves
commute due to the symmetry, so
~ 1 )U (L
U (L ~ 2 ) = U (L
~ 2 )U (L
~ 1 ).

We can diagonalise them to some phase, i.e.,

~ 1 )| i = e−iα1 | i,
U (L

~ 2 ) and U (L
and similarly for U (L ~ 3 ). Hence, there exists some state |~
α, βi such that

~ 1 + n2 L
U (n1 L ~ 2 + n3 L
~ 3 )|~
α, βi = ei~n·~α |~
α, βi.

So without solving anything, we know that

H|~
α, βi = E(~
α, β)|~
α, βi.

Recall that the momentum operator generates translations. So the α

~ i ’s seem like momentum, except that they
are defined from −π to π. Let’s take
αi ≡ Li qi /~.

57
The states are called Bloch waves. Now let’s forget the ~ and take
ψ(x) = ei~q·~x = ei~q·Lj nj ψ → ein·α ψ
~ In other words, acting on the state with translation gives a phase times itself. Also note that
as ~x → ~x + n · L.
shifting
~ j,
~q → ~q + mj Q
which gives
~ l → (~q + mj Q
αl = ~q · L ~ j) · L
~ l,
is equivalent to taking
αl → αl + 2πδjl mj = αl + 2πml .
So we have a dual space made of Q ~ 1, Q
~ 2, Q
~ 3 . You can specify any Q
~ inside this region, and the region is called
the Brillouin zone. In this case we have the energy eigenstates such that
H|~q, βi = Eβ (~q)|~q, βi.
Hence, for each value of ~q, inside the Brillouin zone, we have an infinitely many energy eigenstates, and each
of them is called an energy band. And the band structure is crucial in characterising conductors, semi-conductors,
and insulators.

4.6 Wigner-Eckart Theorem

Suppose we have some J which satisfies the commutation relations of angular momentum, and suppose we have
some state |j, m, αi. Let’s take also |j 0 , m0 , βi. Now, if j 0 6= j, m0 6= m, then the inner product between the two
vanishes. If they were equal, then...

Claim:
hj, m, β|j, m, αi = hj, m − 1, β|j, m − 1, αi.
Proof: We have
J−
|j, m − 1, αi = p |j, m, αi;
~ j(j + 1) − m(m − 1)
J−
|j, m − 1, βi = p |j, m, βi.
~ j(j + 1) − m(m − 1)
Let’s write the latter as
J+
|j, m, βi = p |j, m − 1, βi.
~ j(j + 1) − m(m − 1)
So we also have
J−
hj, m, β| = hj, m − 1, β| p .
~ j(j + 1) − m(m − 1)
Hence,
J−
hj, m − 1, β|j, m − 1, αi = hj, m − 1, β| p |j, m, αi = hj, m, β|j, m, αi. 
~ j(j + 1) − m(m − 1)
In fact, we can generalise it to
hj, m, β|O|j, m, αi = hj, m − 1, β|O|j, m − 1, αi,
~ = 0. It is clear from the manipulation we did above. Next, take O = eiHt/~ . Then [H, J]
as long as [O, J] ~ =0
~ = 0. Recall how probability is represented. The Wigner-Eckart theorem basically tells us that the
gives [O, J]
probabilities
|hj, m, β|O|j, m, αi|2 = |hj, m − 1, β|O|j, m − 1, αi|2 .
We’ll soon see some remarkable consequence.

58
4.6.1 Tensorial Operators

Take the dipole moment operator d~ = q~x, which corresponds to l = 1 in the hydrogen wavefunction. We can
also have the quadruple tensor modes xi xj − 31 δ ij x2 , which corresponds to l = 2, etc. The decay rate is proportional
to the matrix element of the dipole moment,
~
hβ|d|αi.
To find out more about it, let’s first take

Ojm , −j ≤m≤j

to be an operator that’s like a state. We have

 
3 1 1 2 1 1 2
~x = x , √ (x + x ), √ (x − x ) .
2 2
Then here
1
O10 = x3 , O1±1 = √ (x1 ± x2 )
2
are the tensorial operators, i.e., the collection of the three operators. And we have

[J 3 , Ojm ] = m~Ojm .

We also have p
[J± , Ojm ] = ~ j(j + 1) − m(m ± 1)Ojm±1 .
Recall that
J3 = −i~(x1 ∂2 + x2 ∂1 ) = ~(x+ ∂+ − x− ∂− ).
Then,
J+ = ~(−x+ ∂3 + 2x3 ∂− );
J− = ~(x− ∂3 − 2x3 ∂+ ).
Let’s write
hj 00 , m00 , β|Ojm |j 0 , m0 , αi = f (j, j 0 , j 00 , m, m0 , m00 ).
Can we compute f ? We can say that it is a function of β, α, O. Let’s denote the reduced matrix element as

hβ||O||αi.

Now, for any state |∗i consider

Ojm |∗i
and
|j, mi ⊗ |∗i.
We’ll establish a correspondence between the two. Take

J 3 (Ojm |∗i) = J 3 Ojm − Ojm J 3 + Ojm J 3 |∗i = m~Ojm |∗i + Ojm J 3 |∗i.

On the other hand,

J 3 |j, mi ⊗ |∗i = m~|j, mi ⊗ |∗i + |j, mi ⊗ J 3 |∗i.
Thus we see the correspondence. Put it in another way, we can define

Ojm |0i ≡ |j, mi, ~ = 0.

J|0i

Then, commutation is equivalent to action in the sense that

~ Ojm ]|0i = JO
[J, ~ jm |0i = J|j,
~ mi,

and we have
Ojm |j 0 , m0 , αi ↔ |j, mi ⊗ |j 0 , m0 , αi.

59
 Hence, we can think of

hj 00 , m00 , β|Ojm |j 0 , m0 , αi ≡ hj 00 , m00 , β|j, m, j 0 , m0 , αi = Cjj 0 (j 00 , m00 ; m, m0 )hβ||O||αi.

Now, let’s take X

|j 00 , m00 , α) ≡ Cjj 0 (j 00 , m00 ; m, m0 )Ojm |j 0 , m0 , αi.
m,m0
−1 t
Then, because Cjj 0 is a real unitary matrix, i.e., Cjj 0 = Cjj 0 , we have

X
Ojm |j 0 , m0 , αi = Cjj 0 (j 00 , m00 ; m, m0 )|j 00 , m00 , α).
j 00 ,m00

Hence, X
hj 00 , m00 , β|Ojm |j 0 , m0 , αi = Cjj 0 (j 00 , m00 ; m, m0 )hj 00 , m00 β|j̃ 00 , m̃00 , α).
j 00 ,m00

And if j 00 6= j̃ 00 then the whole thing vanishes, so we don’t need to sum. Then,

hj 00 , m00 , β|Ojm |j 0 , m0 , αi = Cjj 0 (j 00 , m00 ; m, m0 )hj 00 , m00 β|j 00 , m00 , α).

Note that consequently,

~ 2 0,±1
|hβ|d|αi| = hj2 , m2 , ∗|Oj=1 |j1 , m1 , ∗i,
which doesn’t vanish only if
|j2 − j1 | ≤ 1.
Hence we have the selection rule
|∆l| ≤ 1.

4.6.2 Isospin

Now, an argument based on quantum gravity says that there cannot be any exact symmetries other than
rotation symmetries (like spin) and gauge symmetries (conservation of electric charge).

Since u and d have similar masses, p = uud and n = udd have similar masses and interactions. This gives rise
to an approximate SU (2) symmetry called isospin. And there is also an SU (3) flavour symmetry involving the u,
d and s quarks. Such approximate symmetries simplify particle classification and properties.

Aside: Since our main aim here is to provide a concrete example of the Wigner-Eckart theorem, for more details
on isospin, particle contents, and relations like 3 ⊗ 3̄ = 8 ⊕ 1, where the in class discussion was not self-contained,
the typesetter decided to just recommend Chapter 9 of the following set of notes, which goes into details of the
representation of su(3). The root diagrams are especially useful to learn, if you have the time. Further, you can
look up Young tableau for the box diagrams (two horizontally placed next to each other: symmetric; two vertically
stacked: anti-symmetric, etc) Prof. Vafa used in class.

http://www.damtp.cam.ac.uk/user/examples/3P2.pdf

We consider the decay processes

∆++ → π + + p,
which has spin
(3/2, 3/2) → (1, 1) + (1/2, 1/2);

60
and
∆+ → π + + n,
which has spin
(3/2, 1/2) → (1, 1) + (1/2, −1/2).
Using the fact that the unitary operator commutes with the isospin, the probability of decaying in time t is
given by,
|hj 00 , m00 , α|U (t)|j, m, j 0 , m0 , βi|2 |Cjj 0 (j 00 , m00 ; m, m0 )|2 1
= = = 3,
|hj 00 , m̃00 , α|U (t)|j, m̃, j 0 , m̃0 , βi|2 |Cjj 0 (j 00 , m̃00 ; m̃, m̃0 )|2 1/3
for top decay to bottom decay. This is the power of the Wiger-Eckart theorem: even if there’s a piece of unknown
information, they are the same in the numerator and denominator and cancels as we only need to know the Cjj 0 ’s.

4.7 Discrete Symmetries

• Parity
In the context of the harmonic oscillator, we discussed parity. The parity operator and its eigenvalue satisfy

P 2 = 1, P = ±1.

~ Then
So we can decompose our states in terms of even and off parities. Take the dipole vector d.
~ −1 = −d,
P dP ~

or,
P d~ = −dP.
~

What’s the probability for a state to go to another state through dipole radiation? We have
~ + βi = h+α|P −1 dP
h+α|d| ~ | + βi = −h+α|d|
~ + βi = 0.

Similarly,
~ − βi = 0.
h−α|d|

Next, take
~ l, mi.
hn0 , l0 , m0 |d|n,

We know that |l − l0 | ≤ 1. In fact, we also have the condition l 6= l0 , since by considering spherical harmonics,
we have
P |n, l, mi = (−1)l |n, l, mi.

So if the two states have the same parity, we get zero. Therefore

|l − l0 | = 1.

Unfortunately, parity is not a symmetry of nature. The Hamiltonian of the universe is not parity invariant,
since only the left-handed electrons interacts. Parity is a good symmetry of the electromagnetic and the
strong interactions, but not a good one of the weak interactions.

• Time Reversal
Entropy aside, time reversal is still not a symmetry of nature. This has to do with anti-unitary operator

T : ψ(t) → ψ ∗ (t).

61
 • Charge Conjugation
Again not a symmetry of nature,
C : e− → e+ .

However, as predicted by relativistic quantum field theory, CTP together is a symmetry of nature.

4.8 Supersymmetry

We discuss supersymmetry in order to solve hydrogen atom! Weinberg uses what’s called the Runge-Lenz vector
symmetry to do this alternate calculation but we’ll proceed with supersymmetry.

Suppose we have a Hilbert space and an operator of order 2, such as the parity operator P ≡ (−)F , which has
eigenvalues ±1. We decompose the Hilbert space as

H = HB ⊕ HF ,

where B corresponds to +1 and F , −1. The operator commutes with the Hamiltonian H, i.e.,

H(−)F = (−)F H.

Now, lets take the operators

Q : HB → HF ;
Q† : HF → HB .
We can diagonalise
(−)F = diag(−1, ..., −1, 1, ..., 1);
H = diag(E1 , ..., En , E10 , ..., En0 ).
Then for some matrix A which may or may not be square, we can write
   
0 A † 0 0
Q= ; Q = ,
0 0 A† 0

such that
(−)F Q = −Q(−)F ; (−)F Q† = −Q† (−)F .
We call Q the supercharge. Now we arrive at the SUSY Hamiltonian, that can be decomposed as follows.

H = QQ† + Q† Q.

It’s easy to check that

[Q, H] = 0.
Notice that
hψ|H|ψi = |Q|ψi|2 + |Q† |ψi|2 ≥ 0.
So if E = 0, then
Q|ψi = 0 = Q† |ψi.
If E > 0, then
6 0,
H|ψi =
†
and either or both of Q|ψi or Q |ψi =
6 0. So we can diagonalise the Hamiltonian as

H = diag(0, ..., 0, E1 , ..., Ek , 0, ..., 0, E10 , ..., Ek0 ).

Let’s take a bosonic state that’s an eigenstate of H, i.e.,

H|ψB i = E|ψB i.

62
 Then since E 6= 0 and Q† |ψB i = 0, we must have

Q|ψB i =
6 0.

Since [H, Q] = 0, we also have

HQ|ψB i = QH|ψB i = EQ|ψB i.
As long as the energy is greater than zero,

Q† Q|ψB i ∝ |ψB i.

So the state comes back to itself up to normalisation. Notice that QQ† is almost the Hamiltonian. In fact, we
do get an eigenstate of the Hamiltonian since the Q† Q piece kills |ψB i. Hence, for every positive eigenvalue, all the
eigenstates are paired up. For each bosonic one, we get a fermionic one, i.e., the number n of bosonic and femionic
excited states equal, but there could be a mismatch for the ground states. In fact, by considering the diagonalised
matrix (−)F , it is easy to see that
nB |E=0 − nF |E=0 = Tr(−)F .
This is called the Witten index, and provides a link between quantum mechanics and topology. Note that even
if we allow A to depend on some parameter so that our Hamiltonian is changed, Witten index doesn’t change, since
for example, if a bosonic state goes up one level, the corresponding fermionic state must go up one level too.

Now let’s discuss an example. Consider the Hilbert space

 
1
H : ψ(x) ⊗ s = .
2

So suppose we are talking about a spin-1/2 particle in one-dimension. Take

(−)F = −σ3 , σ3 = (1, −1).

Take Q and Q† as defined before, and

~ d
A= √ + W (x);
2m dx
~ d
A† = − √ + W (x),
2m dx
where W (x) is real and the momentum-looking term doesn’t have the factor of i so it is anti-hermitian. Then,
substituting the values into H, we have

H = QQ† + Q† Q = diag(AA† , A† A).

So HF and HB don’t mix. We call the spin-up states fermion and the spin-down states boson. We have

~2 d2 ~
AA† = − 2
+ √ W 0 (x) + W 2 ;
2m dx 2m

~2 d2 ~
A† A = − − √ W 0 (x) + W 2 .
2m dx2 2m
Notice that they are of the form
p2
+ V (x).
2m
So we have two particles with different potentials, and yet share the same energy spectrum, except for the
ground state. So let’s consider the ground states. Q|ψB i = 0 corresponds to
 
~ d
√ + W (x) ψB = 0.
2m dx

63
 Then, " r #
Z
2m
ψB = C exp − W (x)dx ;
~
"r Z #
2m
ψF = C exp W (x)dx .
~
The solutions only make sense if they are normalisable. Suppose
R
W (x) = Pn=even → xodd .

Then Tr(−)F = 0 and so it is not normalisable. On the other hand, suppose

R
W (x) = Pn=odd → xeven .

Then Tr(−)F = ±1 and so it is normalisable. Refer to problem set 5 for more details!

5 Time-independent Perturbation Theory

The most general Hamiltonian in a quantum system is not solvable, so we’ll discuss a few approximation
techniques as follows.
• Degenerate and non-degenerate perturbation theories, where we take

H = H0 + H1 ,   1;

• Variational method, which involves guessing wavefunctions and making parameters better;
• Bohn-Oppenheimer approximation, or “integrating out fast variables”, where “fast” refers to, for example,
the fast-moving electrons;
• WKB approximation, where the potential of the system doesn’t vary too much, i.e.,

V (x) ' V0 .

5.1 Non-Degenerate Perturbation Theory

We start with some eigenstates

(0)
H0 |ii = Ei |ii.
We want to solve
(0)
(H0 + H1 )(|ii + δ|ii) = (Ei + δEi )(|ii + δ|ii).
We expand the variations in power series of  as

δ|ii = |ii(1) + 2 |ii(2) + · · · ;

(1) (2)
δEi = Ei + 2 E2 + · · · .
Then,
(0) (1) (2)
(H0 + H1 )(|ii + |ii(1) + 2 |ii(2) + · · · ) = (Ei + Ei + 2 E2 + · · · )(|ii + |ii(1) + 2 |ii(2) + · · · ).

64
 Suppose that for all ,
∞
X ∞
X
i V (i) = W (i) i ,
i=0 i=1

then for all i,

V (i) = W (i) .

• (0) :
(0)
H0 |ii = Ei |ii.

• (1) :
(0) (1)
H0 |ii(1) + H1 |ii = Ei |ii(1) + Ei |ii.

• (2) :
(0) (1) (2)
H0 |ii(2) + H1 |ii(1) = Ei |ii(2) + Ei |ii(1) + Ei |ii.

Now, if we don’t worry about the overall normalisation, then by a choice of normalisation (i.e., rescaling), we
can always assume that the only term proportional to the original state we started with, |ii, is the first term, and
all other terms are orthogonal to |ii. So we can write
X (l)
|ii(l) i = aj |ji,
j6=i

where all |ii(l) ’s are orthogonal.

Let’s now act on the (1) case with the bra hi|. Then
(1)
|ii(1) + hi|H1 |ii = Ei .

hi|H
 0

Hence, the first order change in energy of the ith state is the expectation value of perturbation in that state.
We next act on it with hj|, where j 6= i. Then
(0) (1) 
hj|H0 |ii(1) + hj|Hi |ii = Ei hj|ii(1) + Ei hj|ii.
(0)
Since hj|H0 = Ej hj|, we have
hj|H1 |ii
hj|ii(1) = (0) (0)
.
Ei − Ej
Similarly, we act on the (1) case with the bra hi|. Then,
(2)
hi|H1 |ii(1) = Ei .

From our expression of hj|ii(1) , we can write

X |jihj|H1 |ii
|ii(1) = (0) (0)
.
j6=i Ei − Ej

Hence,
(2)
X hi|H1 |jihj|H1 |ii X |hi|H1 |ji|2
Ei = (0) (0)
= (0) (0)
.
j6=i Ei − Ej j6=i Ei − Ej
(0) (0)
Now, notice that for the ground state, Ei < Ej , so the denominator is negative, and so,
(2)
Egs ≤ 0.

Suppose that the states all have close energies. Then we can write

(2) 1 X 1 1
|hi|H1 |ji|2 = |hi|H12 |ii| − |hi|H1 |ii|2 = hH12 i − |hH1 i|2 .



Egs '
−∆ −∆ −∆
j6=i

65
 Next, the second order equation with hj| acting on it gives
(0) (1) (2)
hj|H0 |ii(2) + hj|H1 |ii(1) = hj|Ei |ii(2) + hj|Ei |ii(1) + 

hj|E
i |ii,

i.e.,
(0) (0) (1)
Ei hj|ii(2) + hj|Hi |ii(1) = Ei hj|ii(2) + Ei hj|ii.
Hence we have, substituting our expression for |ii(1) ,
 
1 X hi|Hi |kihk|H1 |ii hi|H1 |iihj|H1 |ii
hj|ii(2) = (0) (0)

(0) (0)
− (0) (0)
.
Ei − Ej k6=i Ei − Ek Ei − Ej

Note however, that we don’t always have good convergence properties, so going to higher order terms might
not work out. Also, if we take things small, then the first few terms should be enough.

5.2 Degenerate Perturbation Theory

(0) (0)
The previous formulae tell us that if Ei = Ej , then we have infinitely big answers. The assumption of small
 expansion is wrong.

Take the famous Mexican hat potential. The ground state (say, at x2 + y 2 = 1, z = 0, z denoting the energy)
is degenerate. Now, if we place a particle at the ground state y = 1, x = z = 0 and tilt the hat down a bit
along the y−axis towards the +x direction, then the particle will roll all the way to x = 1, y = 0. So even if the
perturbation is tiny, the effect is dramatic if we have degeneracy. To fix this problem, we can start at the position
x = 1, y = z = 0, so that the change of position is 0, although energy goes down.

Let’s go to the second last step of

(0) (0)
hj|ii(1) (Ei − Ej ) = hj|H1 |ii.

Compute H1 in the subspace of the Hilbert space where the eigenvalues are equal. If we diagonalise it, then all
components of the state, when being acted upon by H1 , are going to give results orthogonal to each other. So we
don’t need to worry about the degenerate subspace anymore. Diagonalising H1 corresponds to putting the particle
at the right starting place!

Let’s now discuss some examples.

5.2.1 Zeeman Effect

The Zeeman effect was observed in the 1890s, when atoms are put in a magnetic field. We have

δH = −m ~
~ · B,

where, classically,
e ~
~ =−
m L.
2mc
And we have something similar for the spin part. What’s surprising is that the actual spin part is about double
of what we thought it was, due to a factor of gs = 2.002 · · · , which was first obtained through the Dirac equation.
(You’ll see the whole story when you take QFT!) It turns out that

~ ·L
eB ~ ·S
eB ~
δH = + ge .
2mc 2mc

66
 Suppose we have an electron in an atom like the hydrogen atom, so we have j = l ± 12 . Let’s compute the first
order perturbation of energy.
e ~ + bS|j,
~ m, l, ni · B.
~
δE (1) = hψ|δH|ψi = hj, m, l, n|aL
2mc
We can put the coefficients a and b into a ratio between the two that can be pulled outside. It doesn’t depend
on m thanks to the Wigner-Eckart theorem. Then,
~ + bS|j,
hj, m, l, n|aL ~ m, l, ni = gn,j,l hj, m, l, n|J|j,
~ m, l, ni,

~ m, l, ni is nothing but the Clebsch-Gordon coefficients multiplied by the reduced matrix ele-
where hj, m, l, n|J|j,
~ We next dot it into J~ to get
ment, and similarly for L.
~ · J~ + bS
hj, m, l, n|aL ~ · J|j,
~ m, l, ni = gn,j,l hj, m, l, n|J~ · J|j,
~ m, l, ni,

where
~ · J~ = L
L ~ ·S ~ 2 = 1 [(S
~ +L ~ + L)
~ 2−S ~2 − L ~ 2 = 1 [J~2 − S
~ 2] + L ~2 + L
~ 2 ],
2 2
which gives the eigenvalue
~2
[j(j + 1) − s(s + 1) + l(l + 1)] .
2
~ · J~ gives
Similarly, S
~2
[j(j + 1) + s(s + 1) − l(l + 1)] .
2
1
Taking s = 2 and putting things together, we have

(a − b)l(l + 1) + 43 (b − a) + (a + b)j(j + 1)
gn,j,l = .
2j(j + 1)
Notice that it is in fact independent of n, so with a = 1, b = ge , we have

j(j + 1) − l(l + 1) + 43
gj,l = 1 + (ge − 1) .
2j(j + 1)

~ field,
We call gj,l the Landé g-factor. Indeed, we can always make such a replacement, and for small B
e
δE (1) = gj,l m~B3 .
2me c
~ is much bigger than the hyperfine structure, i.e., the effect of B
If B ~ is much greater than that of S
~ · L,
~ then
starting from
H = H Hydrogen + ~ ·
S
~ (r) + e (L
Lf ~ + ge S)
~ · B,
~
2me c
we can simply go back to the basis of the hydrogen atom where we can take the eigenstates of the original
~ + ge S)
Hamiltonian along with replacing (L ~ ·B
~ with its eigenvalue

(me + ge ms )~B.

5.2.2 Stark Effect

Take the perturbed Hamiltonian

~ · ~x,
H = H0 − e E
since φ = −E~ ·~x. Naively, the first order perturbation vanishes because of parity. Specifically, ~x → −~x under parity,
but the states together is invariant under parity. However, if we have a degenerate case, then we have different

67
l’s. When we diagonalise the Hamiltonian, we get mixed terms which have the same energy. Here’s an example to
make this concrete.

Take n = 1, then we only have l = 0, and j = 1/2. Now, take n = 2. Then we can have l = 0, which gives
j = 1/2 or l = 1, which gives j = 1/2, j = 3/2. So j = 1/2 corresponds to both l = 0 and l = 1, which could in
principle mix. When computing matrix elements, we see that we have off-diagonal pieces involving l = 0 and l = 1
that need to be diagonalised. We ignore the spin for the moment and take E3 for simplicity. Then,

hj = 1/2, l = 0, m = 0 or l = 1, m = 0, ±1|x3 |j = 1/2, l = 0, m = 0 or l = 1, m = 0, ±1i.

We want to compute the expectation value of H1 in the matrix element. Let the first three columns or rows of
a matrix represent the l = 1, m = 1, −1, 0 cases, and the last, l = 0, m = 0.
 
0

 0 0
 α
0 0 α∗ 0
The big block of zero follows from our parity argument. The zero entries at (1,4), (2,4), (4,1), (4,2) are due to
the Wigner-Eckart theorem, which gives

hl = 1, m = ±1|x3 |m = 0, l = 0i = 0.

If we write down the wavefunction, it’s not difficult to compute α explicitly, but we’ll just write down the
eigenvalues here as E = ±α.

5.3 Variational Method

Take any normalised state |ψi, not necessarily an eigenstate of the Hamiltonian. We’ll have

hψ|H|ψi ≥ Egs ,

since the average energy cannot be lower than the ground state energy. So this method is about getting an upper
bound for the lowest energy. Take X
|ψi = an |En i.
n

such that X X
|an |2 = Pn = 1.
n n
X
hψ|H|ψi = Pn En ≥ Egs .
n

Normalising,
hψ|H|ψi
≥ Egs ,
hψ|ψi
and if ψ = ψ(~
α), we have the minimum

hψ(~
α)|H|ψ(~ α)i ∂E
E(~
α) = , = 0.
hψ(~α)|ψ(~
α)i ∂~
α

68
5.3.1 Virial Theorem

The Virial theorem is an application of the variational method. There is a classical analogue, but we deal with
the quantum version here. Take
V (α~ri ) = αk V (~ri ).
For the hydrogen, k = −1; for the harmonic oscillator, k = 2. Suppose we have a bound state which is a ground
state, |ψi.

Claim:
k
hψ|V |ψi.
hψ|T |ψi =
2
Proof: Given some ground state wavefunction, if we vary it, the energy should go up, and the original point must
be critical. Take the trial wavefunction
ψ(~ri , α) ≡ ψ0 (α~ri ).
Then,
dE(α) 
= 0.
dα α=1


Now,
d3~ri ψ ∗ (~ri )V (~ri )ψ(~ri ) d3~ri ψ0∗ (α~ri )V (~ri )ψ0 (α~ri )
R R
1
hV i = = = k hV i0 ,
d3~ri ψ0∗ (α~ri )ψ0 (α~ri )
R R
d3~ri ψ ∗ (~ri )ψ(~ri ) α
since as ~ri → α~ri , we can write
1
V (~ri ) = V (α~ri ).
αk
Similarly,  
~2
d3~ri ψ0∗ (α~ri ) − 2m 2
R
i
∇ i ψ0 (α~ri )
hT i = = α2 hT i0 ,
d3~ri ψ0∗ (α~ri )ψ0 (α~ri )
R

since ∇i is with respect to ~ri and if we want it to be with respect to α~ri , we have to replace it with α∇i . Hence,
1
E(α) = α2 hT i0 + hV i0
αk
So,
dE(α)  k !
= 2αhT i0 − k+1 hV i0 = 0.
dα α=1 α


Hence,
2hT i0 − khV i0 = 0. 
Indeed, this result agrees with the hydrogen atom and the harmonic oscillator. In fact, it is true for the excited
eigenstates of the Hamiltonian too (homework).

Above we derived the Virial theorem through the variational method. There is an easier derivation. We have,
with |ψi an eigenstate of H,
hψ|[Q, H]|ψi = EhQi − EhQi = 0.
Now take an operator
Q = ~x · p~,
where in position space,
p~ = −i~~x∂x ,
and in momentum space,
p~ = i~∂p p = const. + i~p∂p .
Then to find [Q, H] with the Hamiltonian

p2
H= + V (x),
2m

69
we compute the kinetic part as
[p∂p , p2 ] = 2p2 .
Notice that we are basically concluding that the degree of p2 is 2. And for the potential part, by assumption,
the degree is k, or more explicitly,
[~x∂x , V ] = kV.
Hence,
p2
 
2i~ − i~kV = 0,
2m
i.e.,
2hT i − khV i = 0. 

5.4 Bohn-Oppenheimer Approximation

The Bohn-Oppenheimer approximation is based on that heavy things should be left untouched at first approx-
imation. So if we have a molecular problem, we first solve the problem involving electrons only, then involve the
nucleus. In summary, we split a problem into two steps:
1. Solve the problem for fast (light) variable.
2. Include more massive particles.

~ i , M to be the position and mass of the nucleons, and ~ri , m to be those of the electrons. We assume
Let’s take R
that M is infinite and take
X P~ 2 X p~2 X P~ 2
H= i
+ i ~ ≡
+ V (~r, R) i
+ H̃.
i
2M i
2m i
2M
So we now solve
~ j ) = Eα (R)ψ
H̃ψα (~ri , R ~ α (~ri , R
~ j ).
~
The energy spectrum is of course, location-, i.e., R−dependent. ~ as some effective potential
We can view Eα (R)
~
Vα,eff (R). Now, we can always make the expansion
X
~ =
ψ(~r, R) ~ α (~r, R).
fα (R)ψ ~
α

Hence, !
X P~ 2 X
Hψ = i
+ H̃ ~ α (~ri , R
fα (R)ψ ~ i ) = Eψ.
2M i
i α

~ within H̃, assuming small ∂R ψα (r, R), and in particular,

Since there is no derivative with respect to R
1 1
∂R f  ∂R ψα ,
f ψα
then we simply have !
X P~ 2
Hψ = i ~ ~ α (~ri , R
+ Eα (R) fα (R)ψ ~ i ) = Eψ.
2M i
i

Hence, !
X P~ 2
i ~ ~ = Eαi fαi (R),
+ Eα (R) fα (R) ~
2M i
i
or,
~ α (~r, R)
Hfαi (R)ψ ~ = Eαi fαi ψα .

70
 For the second step, we approximate the minimum of the potential as some quadratic potential like the harmonic
oscillator. The approximation is only good for energy close to the minimum. Take the atomic energy

e2 ~2
E∼ , a= ,
a me2
or,
2
me4 e2

E ∼ 2 = mc2 = mc2 α2 .
~ ~c
We are interested in computing the vibrational energy of the molecules. So let’s consider the spring case
2
~2

E ∼ kx2 , x2 ∼ .
me2

Notice the the only length scale is the one involving the Bohr radius. Then the spring constant

E me4 m2 e4
k∼ = .
(~2 /me2 )2 ~2 ~4

Hence, the vibrational energy r r

k m
Evib ∼ ~= mc2 α2 .
M M
p
So comparing to the atomic energy, we have a suppression factor of m/M for the vibrational case. Now, even
if we freeze the molecules, there is still angular degrees of freedom. We have the rotational energy

L2 ~2 ~2 m2 e4 m
Erot ∼ = = = mc2 α2 .
2I M a2 M ~4 M
So the suppression factor is even larger in the rotational case. Let’s now return to the assumption of small
∂R ψα (r, R). How much can R vary before a wavefunction gets exponentially suppressed? We want

R ∂ψ R
ψ(r + R) − ψ(r) ∼ ,  1.
a ∂r a
We have r
Evib ~2
R= ∼ 4/3 1/4 2 .
k m M e
We want to compare R with the atomic scale a = ~2 /me2 . We have

R  m 1/4
∼ ∼ 0.15 < 1,
a M
so the approximation is just ok, not amazing.

5.5 WKB Approximation

WKB approximation is about solving problems assuming that the potential varies very slowly, and the percentage
change in potential should be tiny. It is most elegantly seen in the context of the Feynman path integral.

Aside: Here, just for fun, we present the derivation of the path integral method, as we are already familiar with
all the necessary tools. Setting ~ ≡ 1 for convenience, let’s look at

hxf , tf |xi , ti i = hxf | e−iH(tf −ti ) |xi i.

71
 If we chop the path into N intervals of length , then using the completeness relation
Z
1 = d3 x |xihx|,

we can write
Z N
Y −1
hxf , tf |xi , ti i = d3 x hxf | e−iH |xN −1 ihxN −1 | e−iH |xN −2 i · · · hx1 | e−iH |xi i.
k=1

Now, using the completeness relation

d3 p
Z
1= |pihp|,
(2π)3
we can write, for a typical term,

d3 p
Z
hx0 | e−iH |xi = hx0 |pihp| e−iH |xi,
(2π)3
where 0
hx0 |pi = e−ip·x ,
p2
and for H = 2m + V (x),
h 2 i h 2 i
p p
−iH −i 2m +V (x) −i 2m +V (x) ip·x
hp| e |xi = e hp|xi = e e .

d3 p −ip·(x0 −x) −i 2m p2

Z h i
0 −iH +V (x)
⇒ hx | e |xi = e e
(2π)3
d3 p −i p· x0 −x + 2m
p2
Z h i
+V (x)
= e
(2π)3
d3 p −i 2m
Z h 2 i
p
+V (x)+p·ẋ
≡ e .
(2π)3
If we put things together now, we’ll have
p2
 
−1
Z NY N
Y d3 pl −i f
2m +V (xf )+pf ·ẋN −1
hxf , tf |xi , ti i = d3 xk e
(2π)3
k=1 l=1
p2
   2 
N −1 p1
−i 2m +V (xN −1 )+pN −1 ·ẋN −2 −i 2m +V (x1 )+p1 ·ẋi
×e × ··· × e .

But we can first let p := p̄ − mẋ, which gives

p2 p̄2 1  1 p̄2 1
+ p · ẋ = · mẋ + mẋ2 + 
− 2p̄ ẋ − mẋ2 =
p̄ · − mẋ2 .
2m 2m  2m 2 2m 2
Hence
d3 p̄ −i p̄2 i( 12 mẋ2 −V (x))
Z
0 −iH
hx | e |xi = e 2m e
(2π)3
 3/2
1 2πm 2
ei( 2 mẋ −V (x))
1
=
(2π)3 i
h m i3/2
= eiL(x,ẋ) .
2πi
And now putting things together, we have
−1
h m i3N/2 Z NY
hxf , tf |xi , ti i = lim dxk eiS(xf ,xi ) .
→0 2πi
k=1

72
 -

The idea of the WKB approximation corresponds to the de Broglie wavelength

~
λ= ,
p
where we see that in the limit ~ → 0, we have λ → 0, which means that everything’s almost constant in the limit.
So we are dealing with some kind of classical approximation. Start with some free particle in one-dimension.

ψ(x) = A eipx/~ ≡ A eiS(x)/~ ,

since p and x are taken to be classical and p = p(x). S(x) corresponds to the classical action, and we can take a
power series expansion
S(x) = S0 (x) + ~S1 (x) + ~2 S2 (x) + · · ·
Hence we have
~2 d2
 
2 2
− + V (x) ei[S0 (x)+~S1 (x)+~ S2 (x)+··· ]/~ = E ei[S0 (x)+~S1 (x)+~ S2 (x)+··· ]/~ .
2m dx2

Working out the derivatives, we have

"  2  2 ! #
~2 i ∂S i ∂2S
− + + V (x) = E.
2m ~ ∂x ~ ∂x2

Hence,
2
∂2S

∂S
− i~ = 2m(E − V (x)) = p2 (x).
∂x ∂x2
But if ~ is small, we can ignore the second term. So we get
∂S
' ±p(x),
∂x
i.e., Z x
S(x) = ± dx0 p(x0 ).

And hence we have

dx0 p(x0 )/~
Rx
ψ(x) = A e±i .
This is the first order WKB approximation. Let’s now go beyond linear approximation and write a systematic
one. Using the expansion of S(x), we have

2
∂x S0 + ~∂x S1 + ~2 ∂x S2 + · · · − i~ ∂x2 S0 + ~∂x2 S1 + · · · = p2 (x).

We immediately see that, to the zeroth power in ~,

(∂x S0 )2 = p2 (x).

Hence, Z x
S0 (x) = ± dx0 p(x0 ).

The higher order terms must vanish since the RHS doesn’t contain ~. So we write down order by order the
equations. First order:
2∂x S0 ∂x S1 − i∂x2 S0 = 0,
where the only unknown is S1 , and second order:

2∂x S0 ∂x S2 + (∂x S1 )2 − i∂x2 S1 = 0,

73
where the only unknown is S2 , etc. Let’s first deal with the first order piece. We have

i∂x2 S0 i
∂x S1 = = ∂x log(∂x S0 ).
2∂x S0 2
Hence,
i
S1 = log(∂x S0 ) + c.
2
So to first order, we have
R
dx p/~− 12 log p(x) 1 R
ψ = eiS0 /~+i~S1 /~ = A e±i = Ap e±i dx p/~
.
p(x)

Suppose we have particles of momenta p moving in one-dimension from a lower potential to a higher one. We
have
ψ = A eipx/~ ,
where
number
|ψ|2 ∝ |A|2 = ≡ n,
length
the number density. And the flux
|A|2 p(x)
J ' n · v = |A|2 v = ,
m
where p(x) is not constant as potential is changing. But the number of particles
p cannot change. So we must have
|A|2 p(x) together being independent of x, which makes sense since we had A/ p(x) in our expression for ψ. Let’s
now deal with the second order piece. As above, we easily arrive at

1 dx m2 (∂x V )2
R
1 m∂x V
S2 (x) = − .
2 p3 (x) 4 p5

We have to make sure that ~S2 is small, i.e.,

m∂x V
 1.
~p3

When p(x) = 0, i.e., at turning points, it is not small. Recall that de Broglie wavelength

h
λ(x) = .
p(x)

So the wavelength of the object we are computing varies according to p(x), and we need it to not to vary rapidly.
The amount the wavelength changes over one wavelength is given by
δλ 1 1 ?

∂x λ(x)  1.
= ∆x∂x λ(x) = λ
λ λ λ


We have
h2 h2
λ2 = 2
= .
p 2m(E − V (x))
So
dλ2 h2 dp2 h2
 
dV
=− 4 =− 4 −2m ,
dx p dp p dx
i.e.,
2λdλ h h dV
= 2m 3 .
dx p p dx
Hence indeed we have
δλ
 1.
λ

74
 So in WKB, there is no percentage wavelength change as we move one wavelength. On the other hand, if E < V ,
then
2m(E − V (x)) = p2 (x),
 R 
so p(x) is imaginary. And the exponential exp ±i dx p/~ is real. Let’s define
1p
k≡ 2m(V (x) − E).
~
Then, we have an exponentially rising and falling expression
1 R
ψ ∼ √ e± k dx .
κ
Now, we have solved the problem in individual pieces but cannot connect them together due to the turning
points. But we just need some connecting formulas, which are solutions of
~2 d 2 ψ
− + αxψ = Eψ.
2m dx2
The solutions to these are called Airy functions. For an exponentially rising V (x) where it goes above E at the
point x2 , use Z x2 
2 π 1 Rx
√ cos k dx − ↔ √ e− x2 k dx ;
k 4 k
Z xx2 
1 π 1 R x k dx
√ sin k dx − ↔ − √ e x2 .
k x 4 k
And for an exponentially falling V (x) where it goes below E at the point x1 , use
Z x 
1 Rxx k dx 2 π
√ e 1 ↔ √ cos k dx − ;
k k x1 4
Z x 
1 Rxx k dx 1 π
− √ e 1 ↔ √ sin k dx − .
k k x1 4
WKB approximation is especially applicable to the Bohr-Sommerfeld quantisation and barrier penetration.

5.5.1 Bohr-Sommerfeld Quantisation

Take a potential which rises, then oscillates, then either rises or falls. If it rises, then it won’t be normalisable.
So we adjust the energy so that we’ll only have falling solutions, i.e., bound states. That’s the quantisation of
energy. The condition will end up being the Bohr-Sommerfeld quantisation. We have
Z x2   Z x2 Z x2 
2 π 2 π
√ cos k dx − = √ cos − k dx + + k dx ,
k x 4 k x 4 x
RC RB RC
by A = A + B and cos x = cos(−x). So we require
Z x2
π π
− k dx + = − + nπ,
x1 4 4
i.e., Z x2  
1
k dx = + n π.
x1 2
Now, p = ~k. Hence,
I Z x2 Z x2    
1 1
2 p dx = p dx = ~ k dx = 2~ +n π =h n+ .
x1 x1 2 2
And it relates to the energy since p
p= 2m(En − V (x)).
So the Bohr-Sommerfeld quantisation is justified.

75
5.5.2 Barrier Penetration

Take region I to have V < E, V rising, region II to have V > E, V rising then falling, and region III to have
V < E, V falling. The boundary between I and II occurs at x1 and that between II and III occurs at x2 . Now,
particles come from the left, and we want to know what comes out on the right. We start from the very right, then
when we get to region II,
1 R x k dx 2i − R x k dx
ψII = √ e x2 − √ e x2 .
k k
Now take Rx
2 k dx
r ≡ e x1 .
Then,
x x
r−1
Z  Z 
π 4ir π
ψI = √ sin k dx + − √ cos k dx + .
k x1 4 k x1 4
So the reflection coefficient
 4r − r−1 2  1 − r−2 /4 2 −2 2
     
R =   =  ∼ 1 − 2r ∼ 1 − r−2 .
4r + r−1   1 + r−2 /4  4

And the transmission coefficient Rx

−2 k dx
T = r−2 = e x1
.

6 Time-dependent Perturbation Theory

The time evolution of a state corresponds to the statement

i~∂t |ψ(t)i = H(t)|ψ(t)i.

Recall that for time-independent H,

|ψ(t)i = U (t)|ψ(0)i = eiHt/~ |ψ(0)i.

When H = H(t), we require that

i~∂t U (t) = H(t)U (t).
Let’s first define the time-ordering operator T , such that for any function f (t, ~x),
(
f (t1 , ~x)f (t2 , ~x), t1 > t2
T {f (t1 , ~x)f (t2 , ~x)} = .
f (t2 , ~x)f (t1 , ~x), t1 < t2

Now, it’s important which side H(t) gets pulled down to by differentiation, so we must use the time-ordering
operator T to write
0 0
Rt
U (t) = T e−i 0 H(t )dt /~ ,
where, reminiscent of the path integral derivation we presented in the last section, we chop the time interval from
0 to t into tiny pieces of length  to write
H(t0 )dt0 /~
Rt
e−i 0 = · · · eiH(2)/~ eiH()/~ eiH(0)/~ .

The approximation techniques for the time-dependent cases that we’ll be discussing are the following.
• Sudden time-dependence, where we have the Hamiltonian H0 for t < 0 and a different one, H1 , for t > 0,
where neither is time-depednent;
• H = H0 + H 0 (t), where H 0 (t) is tiny. Here the frequency doesn’t have to be small but the amplitude is small;

76
 • Fluctuating perturbation, where we deal with classical thermal fluctuations. Following from above, we can
write H 0 (t) = H 0 f (t), where we can use Fourier transform to write f (t) = eiωt + e−iωt ;
• Adiabatic perturbation, where H(t) is almost constant, having weak t−dependence. Here the amplitude
doesn’t have to be small but the frequency is small.

6.1 Sudden Time-Dependence

We already know that for t, t0 < 0, we evolve with

e−iH0 (t−t0 )/~ ;

and for t, t0 > 0, we evolve with

e−iH1 (t−t0 )/~ .
For t = 0, there is no evolution since it’s one point in time. The only matching boundary condition is that the
states must be the same. Say we have
H0 |ni = En |ni;
H1 |n0 i = En0 |n0 i.
How do we write the former in the |n0 i basis? Note that we can always write for t < 0,
X
|ψi = an eiEn t/~ |ni.
n

Next, using X
|ni = |n0 ihn0 |ni,
n0

we have X X
|ψ(0)i = an |ni = an hn0 |ni|n0 i.
n n,n0

Hence for t > 0, X X

|ψ(t)i = an |ni = an hn0 |ni e−iEn0 t/~ |n0 i.
n n,n0

6.2 H = H0 + H 0 (t)

Take
H = H0 + H 0 (t),
where H 0 (t) is tiny. To first order we can ignore the second term and write

H0 |ni = En |ni.

Take ωn = En /~. Then we write X

|ψ(t)i = e−iωn t an (t)|ni
n

such that an 6= an (t) when H 0 (t) = 0. So we want to solve

i~∂t |ψ(t)i = (H0 + H 0 (t))|ψ(t)i,

where X
i~(−iωn ) e−iωn t an (t) + i~ e−iωn t ȧn (t) |ni,

LHS =
n

77
and X
En e−iωn t an (t) + e−iωn t an (t)H 0 (t) |ni.

RHS =
n

The first terms from both sides cancel, but we cannot naively drop the sum over n since H 0 (t), which acts on
|ni, is not diagonal. Let’s act on the left with hm|. Then,
X X
hm| i~ e−iωn t ȧn (t)|ni = hm| e−iωn t an (t)H 0 (t)|ni.
n n

Hence, X
i~ e−iωm t ȧm = e−iωn t an (t)hm|H 0 (t)|ni.
n

This is an exact equation with no approximation. Now, we start with perturbation theory where H 0 (t) is small.
We assume that ȧn (t) is small, which is consistent with small H 0 (t). So we can approximate with an (t) ' an (0).
Then, X
i~ȧm (t) = an (0)hm|H 0 (t)|ni e−i(ωn −ωm )t ,
n

which is integrated to Z t
iX 0
am (t) = am (0) − an (0) hm|H 0 (t0 )|ni e−i(ωn −ωm )t dt0 .
~ n 0

For an (0) = δin and m 6= i,

Z t
i 0
am (t) = − hm|H 0 (t0 )|ii e−i(ωi −ωm )t dt0 .
~ 0

Now, going back to the more general case and let’s take H 0 (t) to be of the form

H 0 (t) = U e−iωt + U † eiωt .

Hence,
 Z t Z t 
iX 0 0 0 0
am (t) = am (0) − an (0) hm|U |ni e−iωt −i(ωn −ωm )t dt0 + hm|U † |ni eiωt −i(ωn −ωm )t dt0
~ n 0 0

e−i(ωn −ωm +ω)t − 1 e−i(ωn −ωm −ω)t − 1

 
iX
= am (0) − an (0) hm|U |ni + hm|U † |ni .
~ n −i(ωn − ωm + ω) −i(ωn − ωm − ω)

Now, take an (0) = 0 for all n 6= i, and take ai (0) = 1. Also set m = f . Then,

2 sin(ωi − ωf + ω) 2t −i(ωi −ωf +ω) t 2 sin(ωi − ωf − ω) 2t −i(ωi −ωf −ω) t

 
i
af (t) = − hf |U |ii e 2 + hf |U † |ii e 2 .
~ ωi − ωf + ω ωi − ωf − ω

For ω ∼ ωf − ωi , first notice that

sin x
lim = 1,
x→0 x
and away from 0, it’s oscillatory near the x−axis. Using this, we see that the U term above, instead of the U †
term, is the dominating one. Hence we have
2 t
4 2 sin (ωf − ωi − ω) 2
Pi→f (t) = |af (t)|2 = |hf |U |ii| .
~2 (ωf − ωi − ω)2

Claim:
2 sin2 (αt/2)
lim = δ(α).
t→∞ πα2 t
Proof: First notice that for α away from 0, the expression approaches infinity as t → ∞. Now, using the substitution
u = αt/2, we easily see that
Z ∞
2 sin2 (αt/2)
dα = 1. 
−∞ πα2 t

78
 Hence,
4 πt
Pi→f (t) = |hf |U |ii|2 δ(ωf − ωi − ω).
~2 2
Since E = ~ω, we arrive at
2π
Pi→f (t) = |hf |U |ii|2 tδ(Ef − Ei − E).
~
Hence, the decay rate
dPi→f 2π
Γi→f (t) = = |hf |U |ii|2 δ(Ef − Ei − E).
dt ~
Questa formula importantissima si chiama regola d’oro di Fermi. In general applications, the delta function is
integrated out for a final state as a continuum of states. Notice that the dimension works out here since
[δ] = E −1 , [h i] = E 2 , [~−1 ] = T E −1 .
Now, a particle is a continuum of states. Take normalised eigenstates
1
ψ~n = √ ei~p·~x/~ ,
V
where V = L3 , L being the sides of a periodic cube. So if p~ = ~~k = ~ 2π~ n
L , then summing over final states
corresponds to
L3 d3 p d3 p
Z Z Z
d3 n = 3
= V .
(2π~) (2π~)3
Hence,
2π V d3 p  1 i~p·~x/~ 2
dΓi→f = 3
h√ e |U |ii δ(Ef − Ei − E)
~ (2π~) V
2π 3  1 2
= d ph 3/2
ei~p·~x/~ |U |ii δ(Ef − Ei − E).
~ (2π~)

6.2.1 Hydrogen Atom Ionisation

Now let’s consider the example of ionising a hydrogen atom. We send an electrical wave (whose energy is high
enough) through an electron so that the electrical field pushes the electron free. Take
~ · ~x,
H 0 (t) = eE
where
~ =E
E ~ 0 e−iωt + E
~ 0∗ eiωt , ~ 0 = E x̂3 .
E
Notice that this is in the form
H 0 (t) = U e−iωt + U † eiωt ,
with U = eEx3 . Take the initial state |ii = |n = 1, l = 0, m = 0i to be the ground state
1
ψgs = √ e−r/a .
πa3
Then, Z −i~
p·~
x/~
1 p·~
i~ x/~ 1 −r/a e
h e |U |ii = √ e eEx3 d3 x.
(2π~)3/2 πa3 (2π~)3/2
Its computation without Mathematica is quite possible! It mainly involves is the computation of
Z Z
ei~p·~x/~ f (r)d3 x = eipr cos θ/~ f (r)r2 dr sin θdθdφ
Z
= eikr cos θ f (r)r2 dr(−d cos θ)dφ
Z
2π ikr cos θ 1
= e  f (r)r2 dr
ikr −1
Z
4π
= sin(kr)f (r)r dr.
k

79
 Then by differentiating the above with respect to k3 , using dk dk
3
= kk3 , and setting k3 = k cos θ, we have after
some algebra, √
1 p·~
i~ x/~ −8 2ieE cos θ
h e |U |ii = .
(2π~)3/2 π~3/2 k 5 a5/2
Now, since the delta function imposes energy-momentum conservation, p is fixed up to some angle. So using
dΩ = sin θdθdφ, we have
 2 2 
3 3 3 3 2 ~ k
d p δ(Ef − Ei − E) = ~ d k δ(Ef − Ei − E) = ~ k dΩdk δ − ~ω .
2m

Hence,
dΓ 256e2 E 2 m cos2 θ
= .
dΩ π~3 k 9 a5

6.3 Fluctuating Perturbation

Here, H 0 (t) includes thermal fluctuation, i.e., we are taking classical reasons into account. Using results from
the previous case, we have for f 6= i,

i t
Z
0
af (t) = − hf |H 0 (t0 )|ii ei(ωf −ωi )t dt0 .
~ 0

Hence, Z tZ t
1
|af |2 = hf |H 0 (t1 )|iihi|H 0 (t2 )|f i ei(ωf −ωi )(t1 −t2 ) dt1 dt2 .
~ 0 0
Let t ≡ t1 − t2 . We assume that
Z ∞
gif (t) = hf |H 0 (t1 )|iihi|H 0 (t2 )|f i = g(ω) e−iωt dω.
−∞

Then,
Z Z tZ t
1
2
|af | = dω dt1 dt2 g(ω) e−iω(t1 −t2 ) ei(ωf −ωi )(t1 −t2 )
~ 0 0
Z Z t 2
1 0
= dω g(ω) dt0 ei(ωf −ωi −ω)t
~ 0
4 sin2 (ωf − ωi − ω) 2t
Z
1
= dω g(ω)
~ (ωf − ωi − ω)2
Z
1 πt
= dω g(ω) δ(ωf − ωi − ω).
~ 2
Hence,
∞
d|af |2
Z
2π
Γ= = 2 gif (ω)δ(ωf − ωi − ω)dω.
dt ~ −∞

And finally,
2π
Γ= gif (ωf − ωi ).
~2

80
6.3.1 Radiation Absorption and Emission

Now we consider the example of absorption and stimulated emission of radiation. Take
~
H 0 (t) = eE(t) · ~x.

Assume that the fluctuations of the electric field have an average of the form
Z ∞
Ei (t1 )Ej (t2 ) = δij P(ω) e−iω(t1 −t2 ) dω.
−∞

Since LHS is real and symmetric under the exchange of (t1 , i) ↔ (t2 , j), we have

P(ω) = P(−ω).

The rate of transition is thus

2π 2
Γi→f = e |hf |~x|ii|2 P(ωf − ωi ).
~2
Next, the average energy density of radiation

~2 + B
E ~2 ~2
E
ρ= = .
8π 4π
Since in three-dimensional space δii = 3,
Z ∞ Z ∞
3 3
ρ= P(ω)dω = P(ω)dω.
4π −∞ 2π 0

And using ω = 2πν,

ρ(ν) = 3P(2πν).
Hence,
2πe2
Γi→f = |hf |~x|ii|2 ρ(νfi ).
3~2

6.4 Adiabatic Perturbation

Take a Hamiltonian H(s) where the parameter s = s(t) is a slowly changing function of t, i.e.,

ds(t)
1
dt
For example, we can take
~
H = ασ · B,
such that
s(t) = (Bx (t), By (t), Bz (t)).
We have the energy eigenstates
H(s(t))|n(s)i = En (s)|n(s)i.
Now, take U (s) such that X
U (s)|n(0)i = |n(s)ihn(0)|n(0)i = |n(s)i.
n

Using
H̃(s) = U −1 (s)HU (s),
we have
δij Ei (s) = hj(0)|H̃(s)|i(0)i = hj(0)|U −1 H(s)U |i(0)i = hj(s)|H(s)|i(s)i = δij Ei

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 Next, take
d|ψ(t)i
i~ = H(s(t))|ψ(t)i.
dt
Then,
d
i~U −1 U U −1 |ψi = U −1 H(s)U U −1 |ψi.
dt
And if we set |ψ̃i = U −1 |ψi, then the above becomes

d|ψ̃i dU
i~ = H̃|ψ̃i − i~U −1 |ψ̃i,
dt dt
where the second term is small (but there’s a subtlety: it may become significant after integration). So we have

d|i(0)i
i~ = Ei (s(t))|i(0)i,
dt
which integrates to  Z t 
|ψ̃(t)i = exp −i Ei (s(t0 ))dt0 /~ |i(0)i,
0

i.e.,  Z t 
|ψ(t)i = exp −i Ei (s(t0 ))dt0 /~ |i(s(t))i.
0

6.5 Berry’s Phase

Take a parameter space of parameters sµ . We have that the Hamiltonian H = H(sµ ), and at each parameter
space, we have states of the form |n(sµ )i. As we alter the parameters, these states change to other states, although
we can continuously follow them. Let’s consider the quantity
∂
Aµ ≡ ihn| |ni.
∂sµ
Then, with the hn|ni = 1 normalisation,

∂
A∗µ = −ihn| µ |ni
∂s
←
 
∂
= −i hn| µ  |ni
∂s
"  #
∂ 
 ∂
= −i µ
(hn|ni) − hn| |ni
∂s ∂sµ
= Aµ .

Hence Aµ is a real quantity. Can we choose ∂s∂µ |n(s)i to be orthogonal to |n(s)i? In fact, we can choose to add
a phase to |n(s)i such that the inner product of the two vanishes. Consider

|ñ(s)i = ei(s) |n(s)i.

Then,
∂ ∂(s) ∂
µ
|ñ(s)i = i µ |ñ(s)i + ei(s) µ |ñ(s)i.
∂s ∂s ∂s
Hence we have that
∂ ∂
õ = ihñ| µ
|ñi = Aµ − µ .
∂s ∂s

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 Note that sµ and Aµ play the role of space-time coordinates and Hvector potential, respectively, and the trans-
formation above is the analog of a gauge transformation. Of course, A is gauge-independent. So for every state
in a quantum mechanical problem, if we take it around a loop of parameters, the state comes back to itself up to
a phase, called Berry’s phase. On the other hand, a multidimensional case with many states gives a non-abelian
version of the gauge field.

Now, as in the adiabatic case, take an eigenstate |n(s(t))i. If the t variation is small, then the state will stay as
an eigenstate of the Hamiltonian. Take the evolution of this state, an (t)|n(s(t))i. Then,
 Z t  Z t
En (s(t0 )) 0
 
d
an (t) = exp i dt exp −i hn| |ni ,
0 ~ 0 dt

where the second term is associated with Berry’s phase. It is a useful concept in condensed matter!

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