Quantum Mechanics - I

Lecture-1
Inadequacy of Classical Physics &
Birth of Quantum Physics
Dipan Kumar Ghosh
Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
January 17, 2021

1 Introduction
By the end of the 19th century, physical phenomena known to men could be
reasonably well explained by what we call as classical mechanics, Maxwellian
electromagnetic theory and thermodynamics. The present structure of clas-
sical mechanics, which started with pioneering work of Newton and Galileo,
is primarily due to Lagrange, Jacobi and Hamilton. By the turn of the twen-
tieth century, several situations arose which made physicists to take a closer
look at the concepts explained by the above. Though the departures from
the predictions of classical physics were more pronounced for systems which
were small (such as systems having atomic or molecular sizes,) there were
even situations in macroscopic system for which results of experiment could
not be explained on the basis of the ideas of classical physics. (In addition,
the laws of Newtonian mechanics also broke down when physical systems
travelled with speeds which are not small compared to the speed of light in
vacuum. For instance, even the Galilean velocity addition theorem has to
revised for systems travelling with such velocities. This led to the emergence
of the special theory of relativity, propounded by Einstein, Minkowski and

1
Lorentz. In addition, classical ideas also need to be reformulated when ob-
jects are subject to regions in which gravity is very strong. The departure
from Newtonian mechanics is then subject of what is known as the general
theory of gravitation ).
In the following, we briefly describe a few selected experimental results which
necessitated formulation of a totally new way of looking at the physical world.
It must be emphasized that though the predictions of quantum mechanics
manifest themselves somewhat dramatically for small systems, it remains
valid for all systems, both large and small.

2 Black-body Radiation Spectrum

A black-body is an idealized object which absorbs all radiation that are
incident on it. It can be modelled by a box with its inside walls blackened
and having a small hole in it. Any radiation that enters the body through the
hole gets trapped inside as it undergoes multiple reflection inside the body.

Figure 1: A blackened box with a small hole is a model of a black-body

In order that such an object attains equilibrium it mus also radiate at the
same rate as it absorbs radiation. The radiation is therefore emitted out from
the hole. The radiation from a black-body depends upon the temperature to
which it is raised. The variation of energy density with wavelength of emitted

2
radiation is continuous with the peak shifting towards the lower wavelength
(higher frequencies) side with increasing temperature.

VISIBLE
Spectral energy density u( λ ,T) (arbit units)

14
UV IR
12
5000 K
Classical
10 Theory (5000 K)
Rayleigh−Jeans
8

4
2
3000 K

1 2 3
Wavelength (in µm)

Figure 2: Spectrum of Black-body Radiation

Several attempts have been made to explain the nature of the black-body
radiation spectrum on the basis of classical thermodynamics. In these theo-
ries, radiation is deemed to be emitted from oscillating charged particles on
the surface of the back-body. Such oscillations occur due to thermal motion
of the charged particles. Using thermodynamic arguments and experimen-
tally observed “Stefan’s law”, that the intensity radiated from a black-body
is proportional to the fourth power of its temperature, Wien had obtained
an expression for the energy density of radiation given by

c2 −cb/λT
u(λ, T ) = A 5 e (1)
λ
where A and b are adjustable parameters. The peak values of these curves,
as determined from the above expressions gave the famous law λmax T =

3
constant. While Wien’s law was a good fit at higher frequencies, it failed a
lower frequencies.
Lord Rayleigh looked at the problem anew by considering the radiation field
as a collection of normal modes in a cubical cavity of side L. Since the
radiation is confined, the modes are standing waves which have nodes on the
walls of the cavity. The permitted wave numbers for the modes are

~
E

x=0 x=a

Figure 3: Standing waves in a cavity bounded by walls at x = 0 and x = a

2π 2π πnx
kx = = =
λx (2L/nx ) L
πny πnx
and ky = and kz = . Defining
L L

~n = înx + ĵny + k̂nz ,

we have
4π 2 ν 2 π 2 n2 4π 2 ν 2
k2 = = =⇒ n 2
=
c2 L2 c2
where ν = c/λ is the frequency of the mode. The last equation is the equa-
tion to a sphere of radius 2πν/c. Each distinct set of the positive values
of nx , ny , nz represents one mode of vibration. Since the positive values of
nx , ny , nz lie in an octant, the number of modes in the frequency interval ν
and ν + dν is the volume of the k− space in the interval k to k + dk divided

4
by (π/L)3 , which is the volume occupied by a single point in the k− space.
1 4πk 2 dk
N (ν)dν = ×2×
8 (π/L)3
 3
1 L (2π)3
= × 4π 3 ν 2 dν
4 π c
3 2
8πL ν dν
= (2)
c3

ny
20

15
δρ
ρ
10

0 nx
0 5 10 15 20

Figure 4: Points in nx − ny plane which correspond to a mode inside a box.

ρ is the radial coordinate ρ2 = n2x + n2y + n2z .

A factor of 2 is included in the first line of the above expression to take

into account the two polarization states of the standing wave modes. If the
mean energy of each mode is taken to be kB T , the energy density of radiation
in the frequency interval between ν and ν + dν per unit volume is given by
Rayleigh-Jean’s formula
8πkB T ν 2 dν
u(ν, T )dν = (3)
c3
This expression provided reasonable explanation of the black body spectrum
at low frequencies but diverges in the ultra-violet region. A major problem

5
that arises is when one integrates over all frequencies, it leads to a divergence,
suggesting that the cavity has infinite amount of energy, which came to be
known as the ultraviolet catastrophe.
Planck attempted to provide a theory which smoothly interpolates between
the two extreme limits of frequencies. He took Rayleigh’s expression (2)
but, instead of taking kB T as the mean energy, postulated a different ex-
pression for the average energy which depends on both the temperature and
the frequency of radiation. In his interpolation, the high frequency modes
contributed relatively less to the total energy. His expression for the energy
density was given by
8πν 2 hν
u(ν, T ) = (4a)
c3 ehν/kB T − 1
8πhc 1
u(λ, T ) = 5 hc/λk T (4b)
λ e B −1
where the last equation is the energy density as a function of wavelength.
These equations give the correct high frequency limit (1) and the low fre-
quency limit(3) correctly.
The total energy can be computed as follows
8πh ∞ ν3
Z
E(T ) = 3 dν hν/k T
c e B −1
0 4  Z ∞
8πh kT x3
= 3 dx x (5)
c h 0 e −1

where we have substituted x = hν/kB T . The finite integral above has a value
π 4 /15. The T 4 variation establishes Stefan’s law.
The original derivation of Planck was a mathematical artefact designed to
surmount the problems with Wein’s and Rayleigh-Jean’s formula. Planck
soon provided a justification of his result by making a rather unconven-
tional assumption that the walls of the black body contained many oscillating
charges (resonators) which gave out or absorbed radiation. These resonators
were in thermal equilibrium with the enclosed radiation field, emitting or
absorbing energy. For reasons which had not yet been understood, the en-
ergy exchanged between matter (resonators) and the radiation field was in
units of some minimum energy, i.e. it was quantized. As Gamow observed,
it was like sale of butter – though butter could be produced and stored in
any amounts, it is sold only in units of half pound packets. Thus Planck

6
had made a statement on the amount of energy exchanged between matter
and radiation, with no insight on why it was so. Planck’s derivation of his
formula is messy and is today only of historical interest because of what fol-
lowed thereafter.
Einstein in 1905 made the epoch making proposal that not just the amount
of energy exchanged, but the energy itself is quantized so that a monochro-
matic radiation of frequency ν is an integral multiple of hν. Planck’s formula
is obtained by assuming that the probability of occupation of a mode with
energy nhν is given by the Boltzmann factor at temperature T , so that the
mean energy, instead of being kB T (as would be the case if the modes had
continuous energy E) is given by
P∞ −nhν/kB T
n=0 nhνe
Ē = P ∞ −nhν/kB T
n=0 e
d P∞ −nx
n=0 e
= −hν dxP∞ −nx
n=0 e
hν
= hν/k T (6)
e B −1
where in the second expression above, we had substituted x = hν/kB T .

3 Photoelectric Effect
Einstein used his quanta hypothesis to explain photoelectric effect. The
following facts about photoelectric effect were inconsistent with classical no-
tions:
1. The emission of electrons depends on the frequency of incident radia-
tion. There exists a threshold frequency below which photo-emission
does not take place.
2. When photo emission occurs, the maximum kinetic energy of the emit-
ted electrons, as measured by stopping voltage, depends on the amount
by which the frequency of incident radiation exceeds the threshold fre-
quency.
3. The energy of the photoelectrons do not depend on the intensity of
radiation; the magnitude of the photo current, however, does depend
on the intensity of incident radiation.

7
 4. There is a no perceptible time lag between the instant of shining of
radiation on the metal surface and the emission of electrons, as would
have been the case if the electrons gradually gained energy from the
incident wave before they have enough to overcome the work function.

The explanation of the photoelectric effect as provided by Einstein is that

the incident radiation consists of photons which have energies which are
quantized in units of hν. A single quantum of energy may be absorbed by an
embedded electron, almost instantaneously. A part of the absorbed energy is
spent in liberating the electron from the metal. This is known as the Work
function W , which is given by hν0 , where ν0 is the threshold frequency. The
balance energy is available to the liberated electron as the kinetic energy,
1 2
mv = hν − W = h(ν − ν0 ) (7)
2

4 Compton Effect
Einstein’s explanation of the photoelectric effect essentially brought back
the particle nature of radiation. What it stated is the fact that in spite of
the behaviour of light in interference and diffraction experiments, light in
certain situations behaved like a collection of particles. The particle nature
was further emphasized by the experiments by A. H. Compton in 1923 on
scattering of light by atomic electrons. Compton effect results in an increase
in the wavelength of x-ray and other electromagnetic radiations (such as γ
rays) that have been scattered by electrons. The effect was explained by
assuming that the radiation consisted of quanta of electromagnetic energy
hν with associated momentum hν/c. In Compton effect individual photons
collide with electrons that are loosely bound to atoms. During the process
of collision, the photon transfers a part of its energy and momentum to the
electron as a result of which the recoiling photon has a lower energy and
thereby a higher wavelength. As the energy of X-ray (typically a few keV)
photon is large compared to the binding energy of the electron to the atom,
it is reasonable to consider the electron as free.
The scattering process is illustrated in the figure in which a photon having a
wavelength λi and momentum ~~ki is scattered from an electron, initially at
~λi
rest. The initial energy of the photon is given by ~ωi = . After collision,
c
the photon is scattered at an angle θ with its incoming direction and the

8
electron recoils at an angle ϕ with a momentum ~q. The scattered photon
has a momentum ~~kf .
Scattered photon
λ
f
k kf q
f
λi
θ θ

φ k
ki i

Target electron
(at rest) q

Recoiling electron

The conservation of momentum gives

~ki = ~kf + ~q (8)

which gives
q 2 = (~ki − ~kf )2 = ki2 + kf2 − 2ki kf cos θ (9)
Note that the expression at the centre of the above equation has vectors
~ki and ~kf whereas the last expression is in terms of their magnitudes. For
energy conservation, we use the relativistic expression for energy with m as
the rest mass of the electron
p
~ωi + mc2 = ~ωf + m2 c4 + ~2 q 2 c2
Squaring the above, we get,

~2 c2 q 2 = ~2 (ωi − ωf )2 + m2 c4 + 2~(ωi − ωf )mc2 − m2 c4

= ~2 (ωi − ωf )2 + 2~(ωi − ωf )mc2
= c2 ~2 (ki − kf )2 + 2c~(ki − kf )mc2 (10)

where we have substituted ω = ck. Equation (10) may be written as

2mc
q 2 = (ki − kf )2 + (ki − kf ) (11)
~
Comparing equations (9) with (11) we get

~ 2~ θ
ki − kf = ki kf (1 − cos θ) = ki kf sin2 ( ) (12)
mc mc 2

9
 2π
Substituting k = , we get
λ
2h θ
∆λ = λf − λi = sin2 ( ) (13)
mc 2
h
is known as the Compton Wavelength which, for an electron, has the
mc
value 0.024Å. Compton scattering settled the then ongoing debate, in the
aftermath of Einstein’s explanation of the photoelectric effect, that electro-
magnetic radiation has particle like behaviour.

5 Bohr’s Theory of Hydrogen Atom

In addition to the above mentioned experimental evidence, among the unex-
plained scientific data was the radiation emitted by atoms. To be specific, the
atomic spectra of hydrogen in visible range consisted of wavelengths ranging
from ultraviolet to far infrared. In 1855 Johann Balmer had established an
empirical relation between the frequencies of the emitted lines of hydrogen
spectrum, given by  
1 1 1
=R −
λn 22 n2
where R ' 1.097 × 107 m−1 . Niels Bohr tried to explain the atomic spectra
by making some ad hoc assumptions. In 1911, Rutherford’s experiment on
scattering of alpha particle from a gold foil had led to the conclusion that
most of the atom consisted of empty space with concentration of a massive
nucleus in a small fraction of the atomic volume. However, since the electrons
in the atom are bound to the nucleus by the attractive Coulomb force, the
electrons would be accelerated towards the nucleus. According to the classical
electromagnetic theory, an accelerating charge emits radiation. This would
result in gradual loss of the kinetic energy of the electrons, culminating in
the electrons dropping down on the nucleus. The classical model of the atom
is thus incompatible with the concept of a stable atom. Bohr had made a
set of hypotheses which were consistent with Planck’s idea of absorption and
emission of radiation in discrete (quantized) amounts.
Central to Bohr’s theory was the postulate of stable orbits, according to
which, the electrons occupy only circular orbits having discrete values of
radii. When an electron in such an orbit, it does not radiate energy. However,

10
when the electron jumps from an orbit with a higher radius to an orbit with
a lower radius, it radiates energy, which is given by the difference between
the energies of the two orbits. The frequency of radiation emitted is given by
hν = Eupper − Elower . It follows that if the electron is in the lowest possible
energy state (ground state), the orbit is stable. Bohr determined the allowed
radii of the orbits by assuming that the angular momentum of a stable orbit
is an integral multiple of the Planck’s constant ~, i.e. he radius of an orbit
an is given by
mvn an = mωn a2n = n~
This, along with the fact that the centripetal force is provided by Coulomb
interaction between the electron and the nucleus of charge Ze, gives an ex-
pression for the energy of the n− th orbit

Ze2 Z 2 me4
En = − =− 2 2
2an 2~ n
showing the energy in stable orbits to be discrete. When the electron makes
a transition from the n−th state to a lower state m, the difference in the
energy of the two states appears as the energy of the emItted photon,

En − Em = hνnm

Bohr also formulated what is known as the Correspondence Principle

according to which the new theory must correctly reproduce the valid results
of the older theories in the appropriate limit. In its simple minded form it
implies that the results of classical physics are obtained from quantum me-
chanics in the limit of large quantum numbers. Quantum theory is normally
used to describe the behaviour of bodies that are small in size whereas clas-
sical physics deals with the behaviour of bodies which are macroscopic in
size. The correspondence principle provides a basis for connection between
the new theory and the already existing theory which have been successful
in explaining the physics in a wide variety of systems.

6 Frank - Hertz Experiment

James Franck and Gustav Hertz in 1914 conducted an experiment which con-
clusively established the fact the energy level of Hg atom are quantized and

11
the energy transfer takes place in discrete amounts. In this experiment Mer-
cury vapour is placed in an evacuated chamber which has a cathode and an
anode which is kept at a relative voltage with respect to the cathode. Elec-
trons emitted by the cathode pass through the region of mercury vapour and
can in principle transfer energy to an atom of mercury. The kinetic energy
of the electrons are controlled by the anode voltage. The current- voltage
curve, which in the absence of the mercury atoms should exhibit monoton-
ically increasing behaviour is found to have sudden dips when the kinetic
energy imparted to the electrons is a multiple of 4.9 eV. These peaks and
drops correspond to the multiples of energy difference between the ground
state and the first excited state of the mercury atom. When the electron
imparts 4.9 eV to a mercury atom, the current drops, a second and a third
drop would occur when the electron gives its energy to a send and a third
atom respectively.
When the excited Hg atom returned to the ground state it gives out a radi-
ation of approximately 254 nm corresponding to the energy by which it was
excited. Similar results were also shown for Neon atoms. The experiments
clearly established the fact that electrons in atoms only occupy discrete en-
ergy states.

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One Dimensional Potential Problems

1 Infinite Potential Well (Particle in a box)

Among the one dimensional potential problems, the simplest is known as
the particle in a box problem, also known as the infinite potential well. The
potential is defined by rigid impenetrable walls at both ends, −L/2 ≤ x ≤
+L/2, inside which the potential is constant (taken to be zero) and outside,
the potential is infinite.
L L
V (x) = 0, for − ≤x≤+ (1a)
2 2
L
= ∞, for |x| > (1b)
2

V(x)
oo oo

V(x)=0

x
L/2 L/2
We are interested in finding stationary state solutions to the Schrödinger
equation:
~2 d2 ψ(x)
− + V (x)ψ(x) = Eψ(x) (2)
2m dx2
Outside the well, the potential being infinite, the above equation can only
be satisfied with ψ(x) = 0. Inside the well, the equation becomes

d2 ψ(x) 2mE
+ 2 ψ(x) = 0
dx2 ~
 2mE
Defining k 2 = E, the equation can be written as
~2
d2 ψ(x)
+ k 2 ψ(x) = 0
dx2
which has solutions

ψ(x) = A sin(kx) + B cos(kx)

L
The continuity of the wavefunction at x = ± gives
2
A sin(−L/2) + B cos(−L/2) = 0
A sin(L/2) + B cos(L/2) = 0

By adding and subtracting the above pair of equations, we get

A sin(kL/2) = 0 (3)
B cos(kL/2) = 0 (4)

This pair of equations enable us to divide the solutions into two classes, one
an odd function of x and the other, even function. We have

1. Odd Parity Solutions : B = 0, sin(Lk/2) = 0, the latter condition

gives Lk/2 = nπ, where n is a non-zero integer (n equal to 0 would
make the wavefunction identically vanish). We can also write this
condition as kL = 2nπ, and the wave function may be written as
 nπx 
ψ(x) = A sin (5)
L
where n is an even integer 2, 4, . . .. The normalization of the wave-
function gives the function to be
r
2  nπx 
ψ(x) = sin (6)
L L

2. Even Parity Solutions : A = 0, cos(Lk/2) = 0, the latter condition

nπ
gives Lk/2 = , where n is an odd integer. We can also write this
2
condition as kL = nπ, and the wave function may be written as
 nπx 
ψ(x) = B cos (7)
L

2
 where n is an odd integer 1, 3, . . .. The normalization of the wavefunc-
tion gives the function to be
r
2  nπx 
ψ(x) = cos (8)
L L
Substituting either of these solutions in the Schrödinger equation gives
the energy to be giben by
n2 π 2 ~2
En = (9)
2mL2
Figure below shows the wavefunctions at various energies for n=1,2 and 3
in units of π 2 ~2 /2mL2 .

ψ (x)
2
9
Energy

ψ (x)
1
4

ψ (x)
0
1
0
L/2 L/2

(Wavefunctions plotted against distance

at different values of energies)

2 Finite Potential Well

We will now consider a finite potential well. In order to avoid having to deal
with ±L/2, we will take the width of the well to be 2a with the origin at

3
the centre of the well so that the boundaries of the region are at ±a. The
potential is given by

V (x) = 0, for − a ≤ x ≤ +a (10a)

= V0 , for |x| > a (10b)

V(x)

V=V
0

Region I Region II Region III

V=0 x
a 0 a
We are interested in bound state solutions which requires the energy
eigenvalues must be less than E < V0 . Since V (x) is discontinuous, there
are three regions of solutions, as shown in the figure. Defining
2m
k2 = E (11a)
~2
2m
α2 = 2 (V0 − E) > 0 (11b)
~
we can write the time independent Schrödinger equations in the three regions
as follows

ψI” (x) − α2 ψI (x) = 0 (12a)

”
ψII (x) + k 2 ψII (x) = 0 (12b)
” 2
ψIII (x) − α ψIII (x) = 0 (12c)

Since α2 > 0, the solutions in regions I and III have the form ψ(x) =
Aeαx + Be−αx . In order that the functions in the regions remain square
integrable, we must have ψ(x) → 0 as x → ±∞. Hence the solutions in
these regions are given by

ψI (x) = Aeαx (13a)

−αx
ψIII (x) = Be (13b)

4
The solution in region II is oscillatory and we write it as

ψIi (x) = C sin(kx) + D cos(kx) (14)

The wavefunction and its derivative should be continuous at x = ±a. These

give us a pair of conditions at the boundary of regions I and II and another
pair at the boundary of regions II and III. They are
Regions I & II

Ae−αa = −C sin(ka) + D cos(ka) (15)

−αa
Aαe = Ck cos(ka) + Dk sin(ka) (16)

Regions II & III

Be−αa = C sin(ka) + D cos(ka) (17)

−αa
−Bαe = Ck cos(ka) − Dk sin(ka) (18)

By subtracting (17) from (15), we get

(A − B)e−αa = −2C sin(ka) (19)

and by adding (16) and (18),we get

(A − B)αe−αa = 2Ck cos(ka) (20)

From (19) and (20), we get one class of solution for which either

C = 0 and A = B, or, (21)

α = −k cot(ka) (22)
We can get another class of solution by adding (17) and (15)

(A + B)e−αa = 2D cos(ka) (23)

and subtracting (16) from (18)

A + B)αe−αa = 2Dk sin(ka) (24)

from which we either have

D = 0 and A = −B, or, (25)

5
 α = k tan(ka) (26)
Now, both (22) and (26) cannot be simultaneously satisfied for any real
value of k. Similarly, since all A, B, C and D cannot be simultaneously zero,
whichleads us to the conclusion that the solutions belong to either of the
following classes:

1. Even parity solutions for which A = B, C = 0 and α = k tan(ka).

2. Odd parity solutions for which A = −B, D = 0 and α = −k cot(ka).

Analysis of Solutions:

Even Parity Solutions: Setting A = B and C = 0, we get

ψI (x) = Aeαx (27a)

ψII (x) = D cos(kx) (27b)
−αx
ψIII (x) = Ae (27c)
α
For this set of solutions, we have = tan(ka). Define θ = ka and θ0 =
r k
2mV0
k0 a = a = constant. Using (11b) for α and the expression for k, we
~2
have’ r r
α V0 − E θ02
= = − 1,
k E θ2
which gives the transcendental equation to be solved to be
r
θ02
tan θ = −1
θ2
The figure below shows the interaction of the left hand side of the above
expression with the right.

6
 α /k = θ2
−1
θ02
0 θ= ka
π/2 π 3π/2 θ 0 2π

α 1
If E  V0 , then ∝ and the curve intersects the tangent at a multiple
k θ
bound states. However, as E → V0 , θ → θ0 then the square root approaches
π 2 ~2
that θ axis faster. If θ0 < π, i.e. if V0 < , only one bound state will
2ma2
exist. Note that there is always at least one bound state and that state is
a symmetric state. In the case of infinite square will, the bound states are
nπ nπ
at kn = corresponding to θn = with n = 1, 3, . . . for the symmetric
2a 2
states. Thus the energy and the wave numbers in the present case are lower
than that for the infinite square well potential.
Odd Parity Solutions: Setting A = −B and D = 0, we get

ψI (x) = Aeαx (28a)

ψII (x) = C sin(kx) (28b)
−αx
ψIII (x) = −Be (28c)
α
For this set of solutions, we have = − cot(ka). Using the definition of θ
k
and θ0 ,, the transcendental equation to be solved is given by
r
θ02
cot θ = − −1
θ2
The figure below shows the interaction of the left hand side of the above
expression with the right.

7
 0 θ= ka
π/2 π 3π/2 θ 0 2π
α /k

Once again, larger value of V0 gives rise to more bound states. However,
π π 2 ~2
for θ0 < , i.e. if V0 < , there is no bound state. As noted earlier, in
2 4ma2
this case there is still one bound state, which is the symmetric solution.
Finite potential well finds application in semiconductor lasers in which dif-
ferent materials are sandwiched in such a way that it provides confinement
in the sandwiched layer.

3 Potential Barrier
We will consider now the situation where a particle having an energy E < V0
is incident from left on a finite potential barrier given by

0
 for x ≤ 0
V (x) = V0 > 0 for 0 ≤ x ≤ a (29)

0 for x ≥ a


The classical problem does not provide solution in regions II and III as the
energy of the particle is not sufficient to overcome the potential barrier.

8
 ψ
i

ψ
I II III t

ψ
r
x
0 a
The time independent Schrödinger equations in the three regions are
ψI ” + k 2 ψI = 0 (30)
2
ψII ” − α ψII = 0 (31)
ψIII ” + k 2 ψIII = 0 (32)
where
2mE 2m(V0 − E)
k2 = 2
and α2 =
~ ~2
Solutions of these equations are
ψI = Aeikx + Be−ikx (33a)
αx −αx
ψII = Ce + De (33b)
ψIII = F eikx + Ge−ikx (33c)
Since in region III, there is only a forward moving wave (i.e to the right),
we set G = 0 The corresponding derivatives are
ψI0 = Aikeikx − Bike−ikx (34a)
αx −αx
ψII = Cαe − Dαe (34b)
ikx
ψIII = F ike (34c)
The continuity of the wavefunctions and their derivatives at x = 0 and at
x = a gives
A+B =C +D (35a)
ik(A − B) = α(C − D) (35b)
αa −αa ika
Ce + De = Fe (35c)
Cαeαa − Dαe−αa = ikF eika (35d)

9
Since we are given the incident amplitude A , what we need to do is to get
the reflected amplitude B and the transmitted amplitude F in terms of A.
From (35a) and (35b). we get

C h αi D h αi
A= 1+ + 1− (36a)
2 ik 2 ik
C h α i D h αi
B= 1− + 1+ (36b)
2 ik 2 ik
From (35c) and (35d), we get
 
F ika−αa ik
C= e 1+ (37a)
2 α
 
F ik
D = eika+αa 1 − (37b)
2 α

Substituting (37a) and (37b) in (36a) we get

   
F i F i
A= 1− (1 + ix)eika−αa + 1+ (1 − ix)eika+αa (38)
4 x 4 x

where r
k E
x= = (39)
α V0 − E
The expression (38) for A in terms of F can be simplified as follows

F F
xA = (x − i)(1 + ix)eika−αa + (x + i)(1 − ix)eika+αa
4 4
F F
= i (x − i)2 eika−αa − i (x + i)2 eika+αa
4 4
F ika  2

=i e 2(1 − x ) sinh(αa) − 4ix cosh(αa) (40)
4
Taking complex conjugate of (40), we get

F ∗ −ika 
xA∗ = −i 2(1 − x2 ) sinh(αa) + 4ix cosh(αa)

e (41)
4
Multiplying (40) and its conjugate (41), we get
2
F 4x2
= (42)
A (1 − x2 )2 sinh2 (αa) + 4x2 cosh2 (αa)

10
Substituting for x from (39) and using the relation cosh2 θ − sinh2 θ = 1, we
get for the transmittance
2
F 4E(V0 − E)
T = = (43)
A 4E(V0 − E) + V02 sinh2 (αa)

A similar laborious calculation gives for the reflectance

2
B V02 sinh2 (αa)
R= = (44)
A 4E(V0 − E) + V02 sinh2 (αa)

It may be seen that the sum of reflected intensity and the transmitted in-
tensity is equal to the intensity of the incident beam

R+T =1

This is unlike in the classical case where the height of the barrier being higher
than the energy of the particles, the incident beam is reflected at the barrier.
This phenomenon known as “tunnelling” has several applications. If αa is
large, the positive exponential in the sinh function in the denominator of
(43) dominates and we get the ratio of the transmitted flux to the incident
flux to be
16E(V0 − E) −2αa
T ' e
V02
This is a sensitive function of both the width of the barrier as well as the
amount by which the barrier height exceeds the incident energy.

4 Attractive Delta Function Potential

Consider the attractive delta function potential

V (x) = −aV0 δ(x)

R
Note that, the delta function has the dimension of 1/L because δ(x)dx = 1;
hence the constant aV0 on the right has the dimension of energy times length.
The time independent Schrödinger equation is

~2 d2 ψ ~2 α2
− − aV 0 δ(x)ψ(x) = Eψ(x) ≡ − ψ(x) (45)
2m dx2 2m
where

11
 ~2 α2
E=−
2m
We consider bound state solutions for which E < 0. The potential, as
in the previous cases, has three regions. To the left of the singularity of
potential is region I and to the right is region II, the solutions must be well
behaved in these regions, hence
(
Aeαx Region I
ψ(x) = −αx
(46)
Be Region II

Since the potential is continuous at x = 0, A = B, so that the normalized

wave function is given by
1
ψ(x) = √ e−α|x| (47)
α
We now integrate (45) from − to +, enclosing the singularity,
Z  2 Z 
~2 ~2 α2 
Z
d ψ
− − aV0 δ(x)ψ(x) = − ψ(x)
2m − dx2 − 2m −

Since ψ(x) is continuous, the integral on the right is zero, so that we have

~2 0
− [ψ () − ψ 0 (−)] − aV0 ψ(0) = 0 (48)
2m
[For finite potentials, d2 ψ/dx2 is finite, so that both ψ(x) and its derivative
ψ 0 (x) are continuous. However if the potential has discontinuity, d2 ψ/dx2
is infinite and the first derivative may have a discontinuity]. Using (46) we
have (
Aαeαx for x < 0
ψ(x)0 = −αx
(49)
−Aαe for x > 0
Thus in the limit x = 0− = −, ψ(x)0 = Aα and in the limit x = 0+ = ,
ψ(x)0 = −Aα . The discontinuity in the derivative is

ψ 0 () − ψ 0 (−) = −2Aα

amV0
Substituting this in (48), we get α = , which gives
~2
ma2 V02
E=− (50)
2~2

12
 


 
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LECTURE NOTES ON QUANTUM MECHANICS – Prof. Dipan
K. Ghosh
CHAPTER 13 : ANGULAR MOMENTUM - I

Earlier we had seen that the linear momentum operator p̂ is related to trans-
lation. A finite displacement ~a in space is given by the translation operator
T (~a) = exp(−i~p · ~a/h̄). Translational invariance leads to conservation of lin-
ear momentum. In a similar manner, symmetries with respect to rotation
leads to angular momentum and its conservation.
From our knowledge of classical mechanics, we know that finite rotations do
not commute. However, infinitesimal rotations commute. We will consider
rotation of a system about any axis, say n̂–axis, of the coordinate system.
The sense of rotation will be taken as positive when rotation is anti-clockwise
when viewed from above (i.e. from n–axis, looking towards the origin, the
plane of rotation being perpendicular to the n̂ axis). Starting with a vector
~a, the resulting vector due to rotation by an amount θ about the n–axis is
denoted as
~a0 = R(n̂iθ)~a
Rotation preserves the scalar product of two vectors ~a and ~b as rotation of
each vector by the same angle preserves the angle between the two vectors.
Let us the denote the two vectors by their cartesian components as a column
vector    
ax bx
~a =  ay  ~b =  by 
az bz
The scalar product is given by ~a · ~b = at b, where t stands for the transpose
of the matrix. If R(n̂, θ) is a 3 × 3 rotation matrix, we have,
a0 = R(n̂, θ)a
(at )0 = at R(n̂, θ)
Thus the constancy of scalar product at b = (at )0 b0 gives at b = at Rt Rb so that
Rt R = I
, which shows that the rotation matrix is orthogonal. Since the elements of
the rotation matrix are real, the matrix is also unitary :
R† (θ) = R−1 (θ) = R(−θ)

1
The matrix representation for R is
 
cos θ − sin θ 0
R(ẑ, θ) =  sin θ cos θ 0 
0 0 1

The collection of all rotation matrices form a group SO(3). The rotation
matrices about different axes do not commute, e.g.

R(ẑ, θ1 )R(x̂, θ2 ) 6= R(x̂, θ2 )R(ẑ, θ1 )

However, successive rotations about the same axis commute

R(ẑ, θ1 )R(ẑ, θ2 ) = R(ẑ, θ1 + θ2 ) = R(ẑ, θ2 )R(ẑ, θ1 )

For infinitisimal rotation θ = , neglecting terms Ø(2 )
 
1 − 0
R(ẑ, ) =  + 1 0 
0 0 1

A general infinitisimal rotation may be represented by

 
1 −z +y
R(n̂, ) =  +z 1 −x 
−y +x 1

For small rotation about x, y and z axes, if one retains terms of the order 2 ,
one gets the following matrices :
2 2
1 − 2 0 1 − 2
    
1 0 0 + −
2 2
R(x̂, ) =  0 1− 2 −  R(ŷ, ) =  0 1 0  R(ẑ, ) =  + 1 − 2
2 2
0 + 1 − 2 − 0 1 − 2 0 0

One can check that to order 2 ,

 
0 −2 0
R(x̂, )R(ŷ, ) − R(ŷ, )R(x̂, ) =  2 0 0  = R(ẑ, 2 ) − Iˆ (1)
0 0 0
This relationship will be used later.
From our knowledge of classical mechanics we know that a rotation through

2
 ~ where the rotation is through an angle dΩ about an axis perpendicular
dΩ,
to the plane of rotation, has the evvect of taking the position vector ~r to
~r + d~r, where
~ × ~r
d~r = dΩ
so that
~ × ~r
~r0 = R~r = ~r + dΩ
Going over to quantum mechanics, we wish to find an operator UR (θ), corre-
sponding to a rotation R, which acting on a state | ψi of the system, gives a
state | ψ 0 i. This changes the wavefunction of the system from ψ(~r) to ψ 0 (~r).
Since ψ is a scalar, on rotation ψ(~r) → ψ 0 (~r0 ) so that
ψ 0 (~r0 ) = ψ(~r) = ψ(R(n̂, −θ)~r0 )
Dropping the superfluous primes on r
ψ 0 (~r) = ψ(R(n̂, −θ)~r)
i.e., the wavefunction of the rotated system at the position ~r is the same as
that of the unrotated system at the point
ψ 0 (r) = ψ(R(n̂, −θ)r)
However,
ψ 0 (~r) = UR (n̂, θ)ψ(~r)
= ψ(R(n̂, −θ)~r)
= ψ(~r − dΩ~ × ~r)
~ × ~r) · ∇ψ(~r)
= ψ(~r) − (dΩ
where we have used a Taylor series expansion in the last step and assumed
infinitisimal rotation. Identifying −ih̄∇ as the operator p̂ for momentum, we
have
i ~
ψ 0 (~r) = ψ(~r) − (dΩ × ~r) · p̂ψ(~r)
 h̄ 
i ~
= 1 − (dΩ × ~r) · p̂ ψ(~r)
h̄
 
i ~
= 1 − dΩ · (~r × p̂) ψ(~r)
h̄
 
i ~
= 1 − dΩ · L̂ ψ(~r)
h̄

3
 ~ = ~r × p~,
where L̂ is the operator corresponding to the classical observable L
the orbital angular momentum.
Classically the components of the orbital angular momentum satisfy the Pois-
son bracket relations
{Lz , x} = y {Lz , px } = py
{Lz , y} = −x {Lz , py } = −px
{Lz , z} = 0 {Lz , pz } = 0

i.e.
{Li , xj } = ijk xk
{Li , pj } = ijk pk
where ijk is a rank 3 antisymmetric tensor, which takes the value 1 if the
index ijk is an even permutation of 1,2,3, −1 if it is an odd permutation
and is zero if any two indices are equal. one can define the corresponding
∂
quantum mechanical operators L̂x , L̂y , L̂z by the prescription pi = −ih̄ ,
∂xi
so that
 
∂ ∂
L̂x = −ih̄ y −z
∂z ∂y
 
∂ ∂
L̂y = −ih̄ z −x
∂x ∂z
 
∂ ∂
L̂z = −ih̄ x −y
∂y ∂x

These operators satisfy the commutator relations

[Lx , Ly ] = [ypz − zpy , zpx − xpz ]

= y[pz , z]px + x[z, pz ]py
= ih̄(ypx − xpy ) = ih̄Lz

i.e. the commutation relation between various components of angular mo-

mentum are
[Li , Lj ] = ih̄ijk Lk
which may be put into vector form for operators

L̂ × L̂ = L

4
While the above is a straightforward quantal generalization of the classical
orbital angular momentum, no such classical analogy is available for the spin
angular momentum which is a purely quantum entity. Strictly speaking, a
quantity like L2 which involves components of position and momentum is a
very unlikely candidate for being a constant of motion in quantum mechanics.
In order to provide a common basis for discussion of both spin and orbital
angular momenta, we define angular momentum operator as the generator
of infinitesimal rotation. In analogy with the generator of translation and in
the light of our discussion above, the rotation operator UR (n̂, dθ) is defined
as
i
UR (n̂, dθ) = 1 − (J~ · n̂)dθ
h̄
~
where J is the angular momentum operator. A finite rotation may be built
from infinitisimal rotation
 N
i ~ θ
UR (n̂, θ) = lim 1 − (J · n̂)
N →∞ h̄ N
!
J~ · n̂
= exp −i θ
h̄

Thus the components of Jx , Jy , Jz are generators of infinitesimal rotations.

Since the components of J~ do not commute, the rotation group is not abelian.
Further, we have only considered proper rotations here for which det R = 1.
The collection of all 3X3 real orthogonal matrices form the group O(3).
One can infer the commutation relations between the Ji s from the corre-
sponding rotation matrix representations. For instance, for small angles,
U (x̂, )U (ŷ, ) − U (ŷ, )U (x̂, )
"    2 #"    2 #
i 1 i 2 2 i 1 i
= 1− Jx  + Jx  + . . . 1 − Jy  + Jy2 2 + . . .
h̄ 2! h̄ h̄ 2! h̄
"    2 #"    2 #
i 1 i 2 2 i 1 i 2 2
− 1− Jy  + Jy  + . . . 1 − Jx  + Jx  + . . .
h̄ 2! h̄ h̄ 2! h̄
 2
−i
≈ (Jx Jy − Jy Jx )
h̄
where, we have retained terms upto order 2 . However, we have seen earlier
(equation 1)that the commutator of rotation matrix R is the matrix for

5
rotation about z–axis by 2 minus identity. Thus we expect
 2  
−i i 2
(Jx Jy − Jy Jx ) = 1 −  Jz − 1
h̄ h̄

so that
[Jx , Jy ] = ih̄Jz
Thus we find that

1. Ji is the generator of rotation about the i–th axis.

2. [Ji , Jj ] = ijk ih̄Jk .

Since the components of angular momenta do not commute, only one of them
may be included in the set of commuting operators in a physical problem.
For instance, if we consider a spherically symmeteric Hamiltonian, we have
[Li , H] = 0 for any component Li . However, as [Li , Lj ] 6= 0 for i 6= j, only
one component, say, Lz is taken as a member of the commuting set along
with Ĥ. [exercise : show explicitly that [Lz , V (r)] = 0.
Define
L2 = L2x + L2y + L2z
We can see that L2 commutes with Lz , for

[Lz , L2 ] = [Lz , L2x ] + [Lz , L2y ]

= [Lz , Lx ]Lx + Lx [Lz , Lx ] + [Lz , Ly ]Ly + Ly [Lz , Ly ]
= ih̄(Ly Lx + Lx Ly ) − ih̄(Lx Ly + Ly Lx )
= 0

Further, for a spherically symmetric Hamiltonian [L2 , H] = 0. Thus, for

such a system (like hydrogen atom) Lz , L2 and Ĥ are a set of commuting
operators having simultaneous eigenkets. note that for any state | ψi,

hψ | L2 | ψi = hLψ | Lψi ≥ 0

Further,

hψ | L2 | ψi = hψ | L2x + L2y + L2z | ψi

≥ hψ | L2z | ψi

6
Theorem : A state of zero angular momentum is spherically symmetric and
vice-versa.
Proof : A zero angular momentum is a state for which
Lx | ψi = Ly | ψi = Lz | ψi = 0
Hence !
~ · n̂
L
UR (n̂, θ) | ψi = exp −i θ | ψi =| ψi
h̄
which proves the statement that the state | ψi is unaltered by rotation.
Conversely, if the state is unaltered by rotation,

UR (n̂, θ) | ψi = c | ψi
where c is a constant. Considering infinitisimal rotation about any of the
axes,  
Ln
1 − i  | ψi = c | ψi
h̄
0
i.e. Ln | ψi = c | ψi This is inconsistent with non-commutability of compo-
nents of L unless c0 = 0.

Properties of Angular Momentum

Define
J + = Jx + iJy
J y = Jx − iJy
We can show that the commutation relations satisfied by components of J
are
[J + , J − ] = 2h̄Jz
[J z , J ± ] = ±h̄J ±
Assume that components of J are observables and that Jz | mi = m | mi.
We than have
hm | J + J − | mi = hm | (Jx + iJy )(Jx − iJy ) | mi
= hm | Jx2 + Jy2 − i[Jx , Jy ] | mi
= hm | Jx2 + Jy2 + h̄Jz | mi
= hm | J 2 − Jz2 + h̄Jz | mi (2)

7
Since J 2 and Jz commute, they have common eigenstates | mi. Let us denote
eigenvalues of J 2 as j(j + 1)h̄2 where j is still to be determined,

J 2 | mi = j(j + 1)h̄2 | mi

However, as we had seen in connection with the operator L2 , the eigenvalues

of J 2 are non-negative, so that j is also non-negative.
Hence,
hm | J + J − | mi = j(j + 1)h̄2 − m2 h̄2 + h̄m
However,
hm | J + J − | mi = hJ − m | J − mi ≥ 0
and the equality is applicable, only if, J − | mi = 0. We therefore have,
1 1
j(j + 1)h̄2 − m2 h̄2 + h̄m = j(j + 1)h̄2 − (mh̄ − h̄)2 + h̄2 ≥ 0
2 4
i.e.
1 1
j(j + 1)h̄2 + h̄2 ≥ (mh̄ − h̄)2 ≥ 0
4 2
Define
1 1
j(j + 1)h̄2 + h̄2 = (kh̄ + h̄)2
4 2
where, k ≥ −h̄/2. we then have
 2  2
1 1
k + h̄ ≥ mh̄ − h̄
2 2

so that
−k ≤ mh̄ ≤ k + h̄ (3)
equality is applicable only if J − | mi = 0. Alternatively, using

J − J + = Jx2 + Jy2 − h̄Jz = J 2 − Jz2 − h̄Jz

we get
1 1
j(j + 1)h̄2 − m2 h̄2 − h̄m = j(j + 1)h̄2 − (mh̄ + h̄)2 + h̄2 ≥ 0
2 4
and following reasoning identical to that given above we get

8
  2  2
1 1
k + h̄ ≥ mh̄ + h̄
2 2
which leads to
−k − h̄ ≤ mh̄ ≤ k (4)
where equality applies if J + | mi = 0. From (3) and(4) one concludes that,
the values of k must lie within the range,

−k ≤ mh̄ ≤ +k (5)

where, the left inequality becomes an equality if J − | mi = 0 and the right

inequality becomes an equality if J + | mi = 0.
Note that, using [Jz , J ± ] = ±J ± , we have

Jz J − | mi = (−h̄J − + J − Jz ) | mi
= (−h̄ + mh̄)J − | mi (6)

If J − | mi =
6 0, i.e. from eqn. (3) if m 6= −k, then J − | mi is an eigenstate
of Jz with an eigenvalue (m − 1)h̄. Similarly if (m − 1)h̄ 6= −k, (J − )2 | mi
is an eigenstate with eigenvalue (m − 2)h̄ and so on. Thus the eigenvalues
of Jz are mh̄, (m − 1)h̄, (m − 2)h̄, . . .. This must terminate at −k because of
the inequality (4).
One can use the conjugate relation of (6) , viz.

Jz J + | mi = (m + 1)h̄J + | mi (7)

and obtain a series of eigenvalues mh̄, (m + 1)h̄, (m + 2)h̄ . . .. Thus the

eigenvalues of Jz are

−k, −k + h̄, −k + 2h̄, . . . , k − 2h̄, k − h̄, k

Since the series must terminate on either sides, k itself must be either an
integral multiple of h̄ or of h̄/2. By symmetry these are also eigenvalues of
Jx and Jy . p
We define the value of angular momentum J by k rather than by j(j + 1)h̄.
The possible values of the angular momentum, is therefore,
1 3
0, h̄, h̄, h̄, . . .
2 2

9
We assume J 2 to be an observable, so that k may be taken positive with
r
1 1
k = − h̄ + j(j + 1)h̄2 + h̄2
2 4
Since k = nh̄/2, where n is a positive integer (inclusive of zero)
 2
1 1 1
nh̄ + h̄ = j(j + 1)h̄2 n2 + h̄2
2 2 4
which gives j = n/2. We therefore, summarize as follows :
1. The possible values of the angular momentum are integral or half in-
tegral multiples of h̄/2,viz., 0, h̄/2, h̄, 3h̄/2, . . . corresponding to j =
0, 1/2, 1, 3/2, . . ..
2. For the angular momentum value j, the eigenvalues of J 2 are j(j +1)h̄2 .
3. The eigenvalues of Jz are −jh̄, (−j + 1)h̄, . . . , +jh̄.

Properties of raising (J + ) and lowering (J − ) operators

We will henceforth label the eigenstates of J 2 and Jz by j and m, i.e. | j, mi,
so that
J 2 | j, mi = j(j + 1)h̄2 | j, mi
Jz | j, mi = mh̄ | j, mi
Define a state
| ±i = J ± | j, mi
Now
Jz | ±i = Jz J ± | j, mi
= (±h̄J ± + J ± Jz ) | j, mi
= ±h̄J ± | j, mi + mh̄J ± | j, mi
= (m ± 1)h̄J ± | j, mi
= (m ± 1)h̄ | ±i
Thus | ±i is an un-normalized eigenstate of Jz with an eigenvalue (m ± 1)h̄.
However, such state, by definition, is | j, m ± 1i. Hence, we must have
J ± | j, mi = C± | j, m ± 1i

10
Since both | j, mi and | j, m ± 1i are normaized,

| C± |2 hj, m ± 1 | j, m ± 1i = hj, m | J ∓ J ± | j, mi

Note that

J + J − = J 2 − Jz2 + h̄Jz
J − J + = J 2 − Jz2 − h̄Jz

Thus

| C± |2 = hj, m | J 2 − Jz2 ∓ h̄Jz | j, mi

= j(j + 1)h̄2 − m2 h̄2 ∓ mh̄2
= [j(j + 1) − m(m ± 1)] h̄2

Hence p
C± = (j ∓ m)(j ± m + 1)h̄
Thus
p
J + | j, mi = (j − m)(j + m + 1)h̄ | j, m + 1i
p
J − | j, mi = (j + m)(j − m + 1)h̄ | j, m − 1i

Thus J + , J − (as well as Jx and Jy ) have non-zero matrix elements when the
m values of the states differ by one. Using the above we can obtain a matrix
representation of the angular momentum operators.
Consider j = 1. J 2 has eigenvalues j(j + 1)h̄2 = 2h̄2 . Thus
   
1 0 0 1 0 0
J 2 = 2h̄2  0 1 0  J z = h̄  0 0 0 
0 0 1 0 0 −1

Using p
J + | j, mi = (j − m)(j + m + 1)h̄ | j, m + 1i
we have

J + | 1, 1i = 0
√
J + | 1, 0i = 2h̄ | 1, 1i
+
√
J | 1, −1i = 2h̄ | 1, 0i

11
 +
Thus the matrix of J + with matrix elements Jmm 0 is

 √ 
0 2h̄ √ 0
 0 0 2h̄ 
0 0 0
Similarly, using
p
J − | j, mi = (j + m)(j − m + 1)h̄ | j, m − 1i

we have
√
J − | 1, 1i = 2 | 1, 0i
−
√
J | 1, 0i = 2h̄ | 1, −1i
+
J | 1, −1i = 0
−
The matrix of J − with matrix elements Jmm 0 is

 
√ 0 0 0
 2h̄
√ 0 0

0 2h̄ 0
The matrices for Jx and Jy are given by
   
+ − 0 1 0 + − 0 −i 0
J +J h̄ J −J h̄
Jx = =√  1 0 1  Jy = = √  i 0 −i 
2 2 2i 2
0 1 0 0 i 0

The matrices for the components of angular momentum for j = 1/2 are
h̄
known given in terms of the Pauli matrices σx , σy and σz : Si = σi where
2
     
0 1 0 −i 1 0
σx = σy = Jσz =
1 0 i 0 0 −1

12
 


 
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 Lecture Notes on Quantum Mechanics – Prof. Dipan K. Ghosh

P-402 : Quantum Mechanics – I

Eigenstates of Orbital Angular Momentum – Spherical Harmonics

The components of angular momentum in cartesian coordinates are given by

 
∂ ∂
Lx = −ih̄ y −z
∂z ∂y
 
∂ ∂
Ly = −ih̄ z −x
∂x ∂z
 
∂ ∂
Lz = −ih̄ x −y
∂y ∂x

We will first express these operators in spherical coordinates :

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

so that

r 2 = x2 + y 2 + z 2
y
tan φ =
x
z
cos θ =
r

1
We then have
∂ ∂r ∂ ∂(cos θ) ∂ ∂(tan ϕ) ∂
= + +
∂x ∂x ∂r ∂x ∂(cos θ) ∂x ∂(tan ϕ)
x ∂ zx 1 ∂ y 1 ∂
= − 3 (− ) − 2 2
r ∂r r sin θ ∂θ x sec ϕ ∂ϕ
∂ 1 ∂ 1 sin ϕ ∂
= sin θ cos ϕ + cos θ cos ϕ −
∂r r ∂θ r sin θ ∂ϕ
∂ ∂r ∂ ∂(cos θ) ∂ ∂(tan ϕ) ∂
= + +
∂y ∂y ∂r ∂y ∂(cos θ) ∂y ∂(tan ϕ)
y ∂ yz 1 ∂ 1 1 ∂
= − 3 (− ) + 2
r ∂r r sin θ ∂θ x sec ϕ ∂ϕ
∂ 1 ∂ 1 cos ϕ ∂
= sin θ sin ϕ + cos θ sin ϕ +
∂r r ∂θ r sin θ ∂ϕ
∂ ∂r ∂ ∂(cos θ) ∂ ∂(tan ϕ) ∂
= + +
∂z ∂z ∂r ∂z ∂(cos θ) ∂z ∂(tan ϕ)
2
 
z ∂ 1 z 1 ∂
= + − 3 (− )
r ∂r r r sin θ ∂θ
∂ 1 ∂
= cos θ − sin θ
∂r r ∂θ
Using these, one can express the angular momentum components as follows
 
∂ ∂
Lx = ih̄ sin φ + cot θ cos φ
∂θ ∂φ
 
∂ ∂
Ly = ih̄ − cos φ + cot θ sin φ
∂θ ∂φ
∂
Lz = −ih̄ (1)
∂φ
It may be seen that Lz only depends on the azimuthal angle φ. Using these
expressions for the components of the angular momentum, we can express
L2 as
1 ∂2
   
2 2 1 ∂ ∂
L = −h̄ sin θ + (2)
sin θ ∂θ ∂θ sin2 θ ∂φ2

2
The Laplacian operator, in spherical polar coordinates is given by
∂2 ∂2 ∂2
∇2 = + +
∂x2 ∂y 2 ∂z 2
1 ∂2
   
1 ∂ 2∂ 1 1 ∂ ∂
= 2 r + sin θ +
r ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2
1 L2
 
1 ∂ ∂
= 2 r2 − 2 2 (3)
r ∂r ∂r r h̄
Thus L2 is the angular part of the Laplacian operator. The kinetic energy
operator is therefore, given by,
h̄2 2 h̄2 ∂
 
2 ∂ 1
− ∇ =− r + L2 (θ, φ) (4)
2m 2mr2 ∂r ∂r 2mr2
We will now obtain simultaneous eigenkets of L2 and Lz . These eigenkets will
be denoted by | l, mi. Since L2 and Lz depend only on the angle coordinates,
the coordinate space representation of the eigenfunctions will depend only
on θ and φ. Define
Ylm (θ, φ) = hθ, φ | l, mi (5)
We have
L2 Ylm (θ, φ) = l(l + 1)h̄2 Ylm (θ, φ) (6)
Lz Ylm (θ, φ) = mh̄Ylm (θ, φ) (7)
Using the operator form for Lz in spherical coordinates,
∂
Lz Yl,m (θ, φ) = −ih̄ Yl,m (θ, φ) = mh̄Yl,m (θ, φ)
∂φ
The solution of which is a separation between θ and φ components
Yl,m (θ, φ) = Plm (θ)eimφ
The single valuedness of the wavefunction requires
eim(φ+2π) = eimφ

R 2π= 0, ±1, ±2, . . .. Normalizing

so that m √ the φ component of the wavefunc-
tion Nφ 0 dφ = 1 gives Nφ = 1/ 2π. Thus the azimuthal part of the
wavefunction is given by
1
Φ(φ) = √ eimφ m = 0, ±1, ±2, . . .
2π

3
The eigenvalue equation for L2 can therefore be written as

h̄2 ∂
 
2 2 1 ∂ ∂
L = −h̄ sin θ −
sin θ ∂θ ∂θ sin2 θ ∂φ
L2z
 
1 ∂ ∂
= −h̄2 sin θ +
sin θ ∂θ ∂θ sin2 θ

Thus the eigenvalue equation for L2 is

m2 h̄2
   
2 1 ∂ ∂
2
L Yl,m (θ, φ) = −h̄ sin θ + 2 Yl,m (θ, φ) = l(l+1)h̄2 Yl,m (θ, φ)
sin θ ∂θ ∂θ sin θ
(8)
Introduce a change in variables µ = cos θ, so that
∂ ∂µ d d p d
= = − sin θ = − 1 − µ2
∂θ ∂θ dµ dµ dµ

 
∂ ∂ p
2
d 2 d
sin θ = − 1−µ −(1 − µ )
∂θ ∂θ dµ dµ
2
 
p
2
d 2 d
= − 1 − µ 2µ − (1 − µ ) 2
dµ dµ
so that
h̄2 ∂ 2
 
∂ 2 d 2 d
− sin θ = h̄ 2µ − (1 − µ ) 2
sin θ ∂θ ∂θ dµ dµ
Thus, equation (8) becomes
2
m2 h̄2
 
2 d 2 d
−h̄ 2µ − (1 − µ ) 2 Yl,m (θ, φ)+ Yl,m (θ, φ) = l(l +1)h̄2 Yl,m (θ, φ)
dµ dµ 1 − µ2
The solution cannot depend on φ as the differential equation is with respect to
the variable µ only. Denoting the θ dependent part of Yl,m (θ, φ) as Plm (θ) ≡
Plm (µ), so that the equation above is rewrtitten as follows :
2
m2
 
2 d d
(1 − µ ) 2 Plm (µ) − 2µ Plm (µ) + l(l + 1) − Plm (µ) = 0 (9)
dµ dµ 1 − µ2

The domain of µ is [−1, +1].

~ and L2 are invariant under inversion (x → −x, y → −y, z → −z). In
L

4
spherical polar, this corresponds to θ → π − θ, φ → φ + π. The parity of
Φ(φ) part of the wvefunction is that of eimφ , which, under parity operation
goes to eimπ Φ = (−1)m Φ, i.e. the parity is even if m is even and is odd
if m is odd. The parity of Plm (µ) is to be detrmined. However, since L2
has definite parity, the parity of Plm (µ) is also definite. This may be seen
by an inspection of equation (9). It is seen that Plm (−µ) satisfies the same
equation as Plm (µ).
Equation (9) being a second order differential equation, it has two linearly
independent solutions. Excepting in the case when l is zero or a positive
integer, these solutions diverge at µ = ±1 and are therefore, physically un-
acceptable. For l = 0 or a positive integer, one of the two solutions is finite
and is an acceptable wavefunction.
Physically acceptable solutions which correspond to m = 0 are known as
Legendre polynomials. For m = 0, equation (9) becomes

d2 d
(1 − µ2 ) 2
Pl (µ) − 2µ Pl (µ) + l(l + 1)Pl (µ) = 0 (10)
dµ dµ
Since the point µ = 0 is a non-singular point of the above equation, we seek
a power series solution to (10). The property of the polynomial is described
by a generating function
∞
X
2 −1/2
G(µ, s) = (1 − 2µs + s ) = Pl (µ)sl (11)
l=0

We first show that Pl (µ) defined by (11) satisfies Legendre equation

∂G(µ, s)
= (µ − s)(1 − 2µs + s2 )−3/2 = (µ − s)(1 − 2µs + s2 )−1 G(µ, s)
∂s
so that
∂G
(1 − 2µs + s2 ) = (µ − s)G (12)
∂s
Since
∂G
= s(1 − 2µs + s2 )−3/2 = s(1 − 2µs + s2 )−1 G
∂µ
we have
∂G ∂G
s = (µ − s) (13)
∂s ∂µ

5
ubstitute the expansion of G from (11) in eqn. (12)
∂G X X
(1 − 2µs + s2 ) = (1 − 2µs + s2 ) Pl lsl−1 = (µ − s) Pl s l
∂s l l

Equating coefficients of sl−1 from both sides of above,

lPl (µ) − 2µ(l − 1)Pl−1 (µ) + (l − 2)Pl−2 (µ) = µPl−1 (µ) − Pl−2 (µ)

i.e.,
lPl (µ) − (2l − 1)µPl−1 (µ) + (l − 1)Pl−2 (µ) = 0 (14)
Similarly, substituting (11) in (13) gives
∞ ∞
X
l−1
X ∂Pl (µ)
s Pl (µ)ls = (µ − s) sl
l=0 l=0
∂µ

Equating coefficients of sl−1 from both sides of above gives

∂Pl−1 ∂Pl−2
(l − 1)Pl−1 (µ) = µ − (15)
∂µ ∂µ
In (15), replace l by l + 1
∂Pl ∂Pl−1
µ − = lPl (µ) (16)
∂µ ∂µ
∂Pl−2
Differentiate eqn. (14) with respect to µ and eliminate using (15)
∂µ
dPl dPl−1 dPl−2
l − (2l − 1)Pl−1 − (2l − 1)µ + (l − 1) =0
dµ dµ dµ
i.e.,
 
dPl dPl−1 dPl−1
l − (2l − 1)Pl−1 − (2l − 1)µ + (l − 1) µ − (l − 1)Pl−1 = 0
dµ dµ dµ

which gives, on simplification,

dPl dPl−1
−µ = lPl−1 (17)
dµ dµ

6
Multiply eqn. (16) by −µ and add to (17)
dPl
(1 − µ2 ) = l(Pl−1 − µPl ) (18)
dµ
Differentiate eqn. (18) with respect to µ,
2
 
2 d Pl dPl dPl−1 dPl
(1 − µ ) 2 − 2µ = l − Pl − µ
dµ dµ dµ dµ
= l(−Pl − lPl−1 ) = −l(l + 1)Pl
where, in the last step, we have used eqn. (16). This gives Legendre equation.
It is easy to obtain explicit form for Pl (µ) using the generating function. The
generating function can be simplified using µ = cos θ = (eiθ + e−iθ )/2. In
terms of the angle θ, we can write the generating function as
G(µ, s) = (1 − 2µs + s2 )−1/2
−1/2
= 1 − (eiθ + e−iθ )s + s2


= (1 − seiθ )−1/2 (1 − se−iθ )−1/2

Using a binomial expansion
  
1 iθ 3 2 2iθ 5 3iθ 1 −iθ 3 2 −2iθ 5 −3iθ
G(µ, s) = 1 + se + s e + e + . . . 1 + se + s e + e + ...
2 8 16 2 8 16
3 1 5 3
= 1 + s cos θ + s2 cos 2θ + s2 + s3 cos 3θ + s3 cos 3θ + . . .
4 4 8 8
1 1
= 1 + s cos θ + (1 + 3 cos 2θ)s2 + (5 cos 3θ + 3 cos θ)s3 + . . .
4 8
so that
P0 (cos θ) = 1
P1 (cos θ) = cos θ
1
P2 (cos θ) = (3 cos2 θ − 1)
2
1
P3 (cos θ) = cos θ(5 cos2 θ − 3)
2
where we have used expansions of cos 2θ and cos 3θ in terms of cos θ. An
useful formula to generate the Legendre polynomials is Rodrigue’s formula
1 dl 2
Pl (µ) = (µ − 1)l
2l l! dµl

7
The polynomials are sketched below as a function of µ = cos θ. Pl has l zeros
in the domain [−1, +1] and satisfies orthonormality condition
Z 1
2
dµPl (µ)Pm (µ) = δml
−1 2l + 1

P (x)
0 1

P (x) P (x)
4 1
0.5

P (x)
5
0.5 P (x) P (x)
2 3

The solutions of eqn. (9) for m 6= 0 are called associated Legendre functions
and the eigenfunctions of the L2 operator, including the azimuthal part are
known as Spherical Harmonics. It can be shown that solutions exist only for
| m |≤ l, a condition which is satisfied by the angular momentum quantum
numbers. It can be shown that the associated Legendre functions are related
to the Legendre polynomials through

d|m| Pl (µ)
Plm (µ) = (1 − µ2 )|m|/2
dµ|m|

8
Writing the associated Legendre functions Plm (µ) as
Plm (µ) = (1 − µ2 )|m|/2 u(x)
and using the above relationship with the Legendre polynomials, one can
obtain a Rodrigue’s formula for u(µ)
1 dl+|m| 2
U (x) = l l+|m|
(µ − 1)l
2 l! dµ
showing u(µ) to be a polynomial of degree l− | m |. The normalized eigen-
functions of L2 are given by
Ylm (θ, φ) = Nlm Plm (cos θ)Φ(φ)
 1/2
2l + 1 (l− | m |)!
= C Plm (cos θ)eimφ (19)
4π (l+ | m |)!
where C = (−1)m for m > 0 and = 1 for m ≤ 0. Some of the spherical
harmonics are listed below :

symbol l = m = Ylm =
1
Y00 0 0 √
4π
r
3
Y10 1 0 cos θ
r 4π
3
Y1,±1 1 ±1 ∓ sin θe±iφ
8π
r
5
Y20 2 0 (3 cos2 θ − 1)
r16π
15
Y2,±1 2 ±1 ∓ sin θ cos θe±iφ
r 8π
15
Y2,±2 2 ±2 sin2 θe±2iφ
32π

Note that the azimuthal part has parity of | m |, e.g.,

e±i(φ+π = e±iπ e±iφ = (−1)e±iφ
e±2i(φ+π = e±2iπ e±2iφ = e±2iφ

9
whereas Pml (cos θ) has parity of l− | m | because Plm (cos θ) is an even
function (1 − µ2 )|m|/2 multiplied by a polynomial in µ which has parity of
l− | m |. Thus the spherical harmonic Yl,m (θ, φ) has the parity of l.

10



 
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 Quantum Mechanics - I
Lecture-18
Landau Levels and Integer Quantum
Hall Effect
Dipan Kumar Ghosh
Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
June 6, 2020

1 Introduction
In this lecture we will discuss the classic work of Lev Landau (1908-1968)
on the quantum mechanics of the motion of an electron in the presence of a
magnetic field. The work became all the more important after the discovery
by Klitzing in 1980 of what came to be known as the Quantum Hall Effect
(QHE). We will begin by a brief description of the classical Hamiltonian and
then discuss the quantum mechanical formulation. At the end, we will give
a very brief description of the quantum Hall effect and the application of
the quantum mechanical solution of the electrons in a magnetic field for this
problem.

2 Classical Hamiltonian
We take the magnetic field to be in the −z direction and e, the electron charge
to be negative, so that eB > 0. For the moment we take the electron to be
confined in the x-y plane, the motion in the z-direction can be subsequently
superposed. As the magnetic field does no work on the electron, the speed

1
of the electron does not change and is given by equating the centrifugal force
to the Lorentz force acting on the electron

mv 2 qvB
=
R c
which gives the “cyclotron radius” R to be given by
mvc
R= (1)
qB
The electron moves in a circular path of radius R with a frequency known as
the “cyclotron frequency” given by
eB
ωc = (2)
mc
In the presence of an electromagnetic field defined by the scalar potential φ
~ the classical Hamiltonian is given by
and a vector potential A,

1 eA~
H= (~p − )2 + eφ (3)
2m c
The choice of φ and A ~ are not unique. The problem clearly has translational
symmetry in x and y directions. In addition, it has rotational symmetry for
rotation about the z-axis. However, no single choice of a gauge brings out
all these invariances. A popular choice is the symmetric gage in which
~ = −y î + xĵ
A (4)

which preserves the rotational symmetry but not the translational symme-
try. The Landau gauge, which was originally used by Landau in solving the
problem is
~ = Bxĵ
A (5)
which preserves translational symmetry in the y-direction and the gauge
~ = −By î
A

maintains translational symmetry in the y-direction. [ The gauges differ by

gradient of a scalar function. For instance, the symmetric gauge may be
B
obtained from Landau gauge by adding a terms ∇(xy).] The classical
2
2
Hamiltonian given by (3) can be used to provide solution for the Hamilton’s
equations of motion
∂H
q̇i = (6)
∂pi
∂H
ṗi = − (7)
∂qi

where ~q = {qi } = (x, y, z) and p~ = {pi } = (px , py , pz ). Taking the x−

component, we have
 
∂H 1 eAx
ẋ = = px −
∂px m c
     
∂H e eAx ∂Ax e eAy ∂Ay e eAz ∂Az ∂φ
ṗx = − =− px − − py − − pz − −e
∂x mc c ∂x mc c ∂x mc c ∂x ∂x
!
e eA~ ~
∂A ∂φ
=− p~ − · −e
mc c ∂x ∂x

Similar equations can be obtained for the other components as well and we
have
 
1 eAi
q̇i = pi − (8a)
m c
!
e eA~ ~
∂A ∂φ
ṗi = − p~ − · −e (8b)
mc c ∂qi ∂qi

Taking a second derivative, we get for the acceleration

 
1 e dAi
ai = q̈i = ṗi −
m c dt

Substituting for ṗi we have

!
e eA~ ~ e dAi
∂A ∂φ
mai = p~ − · − −e (9)
mc c ∂qi c dt ∂qi

3
We will rewrite the second term containing the total time derivative of Ai as
follows:
dAx ∂Ax dx ∂Ax dy ∂Ax dz ∂Ax
= + + +
dt ∂x dt ∂y dt ∂z dt ∂t
∂Ax ∂Ax ∂Ax ∂Ax
= vx + vy + vz +
∂x ∂y ∂z ∂t
∂Ax
= ~v · ∇Ax +
∂t
Substituting the above in the expression (9), we can rewrite it as
!
e eA~ ~ e
∂A
mai = p~ − · − (~v · ∇)Ai + eEi (10)
mc c ∂qi c

where we have substituted

~
~ = −∇φ − 1 ∂ A
E
c ∂t
Substituting the expression for velocity from (8a), we get, for the acceleration

e ∂A ~ e
mai = ~v · − (~v · ∇)Ai + eEi (11)
c ∂qi c
Consider the first two terms of the above equation. Consider qi = x

e ∂A ~ e e

∂Ax ∂Ay ∂Az
 
∂Ax ∂Ax ∂Ax

~v · − (~v · ∇)Ax = vx + vy + vz − vx + vy + vz
c ∂x c c ∂x ∂x ∂x ∂x ∂y ∂z
    
e ∂Ay ∂Ax ∂Az ∂Ax
= vy − + vz −
c ∂x ∂y ∂x ∂z
e e ~ x
= [vy Bz − vz By ] = (~v × B)
c c
Thus, the expression (11) for the force on the charged particle in the electro-
magnetic field becomes
e ~ + eE
~
m~a = (~v × B) (12)
c
which is the correct expression for the Lorentz force. We will now go over to
the quantum mechanical formulation of the problem.

4
3 Going Over to Quantum Mechanics - Lan-
dau Levels
Having established that the classical Hamiltonian given by (3) describes the
behaviour of a charged particle in an electromagnetic field, we will be looking
for a solution of the corresponding quantum mechanical Schrödinger equa-
tion. We have !2
∂ψ 1 eA~
i~ = −i~∇ − ψ + eφψ (13)
∂t 2m c

We will choose a symmetric gauge in which A~ = B (−y, x, 0). For the time
2
being we will choose φ = 0. We define new variables
Be
Πx = px + y
2c
Be
Πy = py − x
2c
Πz = pz (14)
r r
c c
It may be checked that Πx and Πy are canonically conjugate be-
Be Be
cause
Be Be Be Be Be
[Πx , Πy ] = [px + y, py − x] = (−[px , x] + [y, py ]) = (i~+i~) = i ~
2c 2c 2c 2c c
Thus r r
c c
[ Πx , Πy ] = i~
Be Be
However Πz commutes with both Πx and Πy . In terms of these variables the
Hamiltonian becomes
Π2 Π2y Π2
H= x + + z (15)
2m 2m 2m
Π2z p2z
It may be observed that the Hamiltonian commutes with = . As
2m 2m
2
p
a result, the eigenstates of the Hamiltonian are also eigenstates of z , the
2m
~2 kz2
latter having energy . The motion in z- direction is that of a free particle.
2m

5
Let us define two new operators
c
b= (Πx + iΠy ) (16a)
2Be~
c
b† = (Πx − iΠy ) (16b)
2Be~
Using the commutation relations of Πx and Πy given above, it is easy to show
that
[b, b† ] = 1 (17)
It may be seen that
c c
bb† = (Πx + iΠy )(Πx − iΠy ) = (Π2 + Π2y − i[Πx , Πy ])
2e~B 2e~B x
c c e~B c 1
= (Π2x + Π2y ) + × = (Π2x + Π2y ) +
2e~B 2e~B c 2e~B 2
Thus the Hamiltonian (15) becomes

Π2 Π2y Π2 p2z
 
2e~B † 1
H= x + + z = bb − +
2m 2m 2m 2mc 2 2m
2
1 p
= ~ωc (b† b + ) + z (18)
2 2m
where
eB
ωc =
mc
is the electron cyclotron frequency. The energy levels, apart from the free
motion in the z-direction are given by those of one dimensional harmonic
oscillator,  
1
En = n + ~ωc (19)
2
These energy levels are known as Landau Levels. The cyclotron motion is
confined in the x-y plane while the z-direction is free. There is something
strange about the above result. We had a two dimensional problem to begin
with. However, we have mapped it to a one dimensional problem, thereby
losing one degree of freedom. The reason could be attributed to the fact
that unlike the case of the harmonic oscillator, each energy level does not
correspond to a unique state, rather there are degeneracies associated with
the energy levels, which we will explore in the next section.

6
A comment on the spin of the electrons is appropriate. In the above dis-
cussion, we have neglected the spin of the electrons. Electrons placed in a
magnetic field have different energies for different values of their spin and
orbital angular momenta. For free electrons, the g− factor is 2. The up spin
electrons are raised in the energy and the down spins lowered, with their
e~
energy difference being B = ~ωc . Thus the energy of up spin electrons
mc
in the n− th level is precisely equal to that of down spin electrons in the
(n + 1)− th level. This does not actually happen in real materials because of
band structure effects, which results in Zeeman splitting being much smaller.
Thus in practice, for GaAs the n = 0 spin up levels will fill up first, followed
by n = 0 spin down and alternating thereafter. This is schematically shown
in Fig. 1.

n=3 gµ B
Β

hω
n=2 gµ B
Β

hω
n=1 gµ B
Β
hω
n=0 gµ B
Β

Figure 1: Landau Energy levels including Zeeman splitting - in practice,

Zeeman splitting is much smaller.

4 The Ground State

We define the ground state of the Landau levels by the action of the ladder
operator Π on the ground state
b | 0i = 0 (20)
Inserting the definition of b in terms of Πx and Πy vide equations (16b)
c
(Πx + iΠy ) | 0i = 0
2Be~
7
Reverting to the momentum and position variables, using (14)

c Be Be
(px + y + ipy − i x) | 0i = 0 (21)
2Be~ 2c 2c
It is convenient at this stage to go over to complex variables z = x + iy, z̄ =
x − iy. This gives the following relations

z + z̄ z − z̄
x= ; y=
2 2i
∂x 1 ∂x 1
= ; =
∂z 2 ∂ z̄ 2
∂y 1 ∂y 1
= ; =−
∂z 2i ∂ z̄ 2i
∂ 1 ∂ 1 ∂ ∂ 1 ∂ 1 ∂
= − i ; = + i
∂z 2 ∂x 2 ∂y ∂ z̄ 2 ∂x 2 ∂y
∂ ∂ ∂ ∂ ∂ ∂
= + ; =i −i
∂x ∂z ∂ z̄ ∂y ∂z ∂ z̄

Using the above variable transformation (21) becomes

r
c Be Be
(px + y + ipy − i x) | 0i = 0
2Be~ 2c 2c
 
∂ ∂ Be
−i~ +~ + (y − ix) ψg (z, z̄) = 0
∂x ∂y 2c
 
∂ ∂ Be
+i + (x + iy) ψg (z, z̄) = 0
∂x ∂y 2c~
 
∂ Be
2 + ψg (z, z̄) = 0 (22)
∂z 2c~

The equation (22) can be solved by an ansatz

eB
ψg (z, z̄) = exp(− z z̄)f (z, z̄) (23)
4c~
Substituting the above ansatz into (22), we get

∂ eB eB eB ∂
ψg (z, z̄) = − z exp(− z z̄)f (z, z̄) + exp(− z z̄) f (z, z̄) = 0
∂ z̄ 4c~ 4c~ 4c~ ∂ z̄

8
Substituting this in (22), we get

eB eB eB ∂ eB
− z exp(− z z̄)f (z, z̄) + exp(− z z̄) f (z, z̄) + zψ(z, z̄) = 0
4c~ 4c~ 4c~ ∂ z̄ 4c~
The first and the last terms of the above cancel, resulting in f (z, z̄) satisfying

∂
f (z, z̄) = 0 (24)
∂ z̄
Thus, f (z, z̄), as a function of z̄ is a constant. Assuming that as a function
of z itself, it is an analytic function of z. For instance, any polynomial
in z would satisfy this equation. This is different from the solution of the
harmonic oscillator, where it is a Hermite polynomial. Take the ground state
to be labeled by an index m, so that the wavefunction ψg (z, z̄) may be written
as
eB
ψg (z, z̄) = z m exp(− | z |2 ) (25)
4c~
Note that the values of m must only be non-negative integers, as negative val-
ues of m would make the function ill behave near origin and fractional values
would make it multi-valued. Thus the ground state has infinite degeneracies
corresponding to different values of m. We will see later that confinement in
the x-y plane gives rise to finite degeneracies.
Recalling that Rthe motion is two dimensional, we can normalize the wave-
function using ψ ∗ (z, z̄)ψ(z, z̄)d2 r = 1. Taking

eB
ψg (z, z̄) = Nm z m exp(− | z |2 )
4c~
we have
Z ∞ Z ∞  m+1
2 2m eB 2 2c~
Nm r exp(− 2πrdr = Nm π m! = 1
−∞ −∞ 2c~ eB

Thus the normalization constant is given by

"  m+1 #−1/2
2c~
Nm = πm! (26)
eB

9
5 Landau Gauge Formulation
While the physics of choosing one gauge or another remains the same, the
intermediate calculations do not remain invariant. Note that the magnetic
field in the z-direction is invariant under rotational symmetry in x-y plane and
has a translational symmetry, the choice of gauges do not. The symmetric
gauge preserves only the rotational invariance. A choice which preserves
translational invariance along the y-direction is “Landau gauge” in which
A~ = (0, Bx, 0). Because of this, we can look for energy eigenstates which
are simultaneous eigenstates of py , i.e which have the form eiky y f (x, ky ). The
Schrödinger equation for this case may be written as
"  2 #
1 eBx
H= p2 + py − + p2z − eφ(z)
2m x c

p2
Apart from py , H also commutes with z − eφ(z). We look for simultaneous
2m
eigenstates for all the three,
 2 
pz
Hψ = Eψ, py ψ = ~ky ψ, − eφ(z) = Ez ψ
2m
We thus rewrite the Schrödinger equation as
"  2 #
1 eBx
p2 + ~ky − ψ = (E − Ez )ψ
2m x c

~ky c
Define x0 = the equation becomes
eB
e2 B 2
 
1 2 2
p + 2 (x − x0 ) ψ = (E − Ez )ψ
2m x c
eB
Using ωc = ,
mc
1  2
px + ωc2 (x − x0 )2 ψ = (E − Ez )ψ

(27)
2m
The above equation represents a one dimensional harmonic oscillator with its
centre at x = x0 . The presence of x0 has no effect on the energy eigenvalues

10
because both x and x − x0 are canonically conjugate to px . Thus The energy
eigenvalues are
1
E = Ez + ~ωc (n + )
2
where n = 0, 1, 2 . . .. the ground state would be
2
ψg = Nm e−α(x−x0 ) (28)

6 Degeneracy of the Ground State

We have seen that the energy is independent of the position of the centre of
the oscillator, thereby making it independent of ky . This leads to degeneracy.
Let us set kz = 0. Consider a two dimensional system of dimension Lx × Ly .
Translational symmetry in the y-direction requires eiky y = 1 i.e
2π
ky = ny
Ly
where ny = 0, 1, 2 . . .. However, ny has to have a maximum because ky has
a maximum value corresponding to the maximum number of states. There
is no translational symmetry in the x-direction. The centres of the cyclotron
orbits are restricted to lie within the sample, i.e 0 ≤ x0 ≤ Lx . Thus
~ky c
0≤ ≤ Lx
eB
Thus the number of degenerate states is
Ly Ly eBLx BA
N = (ny )max = (ky )max = × =
2π 2π ~c ch/e
We define flux quantum Φ0 by
ch
Φ0 = (29)
e
in terms of which the ground state degeneracy works out to
BA
N= (30)
Φ0
Flux quantum is a constant and has a numerical value given by
Φ0 = 4.13 × 10−15 T − m2 = 4.13 × 10−7 G − cm2

11
6.1 Excited States
The excited states of the system are obtained by action of the raising oper-
ators (b† )n on the ground state of the system. The energies would be found
to be given by given by the same expression as for the harmonic oscillator.
It is also easy to show that the degeneracy of each Landau level is the same.

7 Hall Effect
The basic geometry of a Hall effect experiment is shown in Fig. 2. Consider
a thin slab of width w and thickness t. An electric field E~ = Ex î is applied
along the length of the sample. This causes the charge carriers q (assumed
~ = B k̂ is applied
positive) to drift along the x-direction. A magnetic field B
perpendicular to the surface of the sample, causing the charge carrier to
bend along −y direction. This results in an accumulation of positive charges
along one edge and negative charges along the opposite edge. Since charges
cannot move out of the sample, the force on charge carriers due to the electric
field created by the charge separation must exactly balance the Lorentz force
q ~ on the carriers. Thus if the resulting transverse voltage (called the
~v × B
c
Hall voltage) is denoted by VH , we must have
qVH qvB
=
w c

x
z
B

+
+
y +
+
+
+
+ +
+
t

V
H

Figure 2: Geometry of Hall Effect

12
 Thus the Hall voltage is given by
vBw
VH = (31)
c
The Hall resistance is the ratio of the transverse voltage and the current.
In three dimensions, if the density of the charge carriers is n, the current is
the product of the current density qnv with the cross sectional area wt, i.e.
I = qnv(wt), so that
VH B
Rxy = = (32)
Ix cqnt
The Hall resistivity is then obtained by dividing the Hall resistance by ap-
propriate geometrical factors.
However, in two dimensions, the Hall resistance is devoid of any geomet-
rical factor because the current density is current per unit length so that
I = (qvn)w
VH B
Rxy = = (33)
Ix cqn
Because of this reason, in two dimension, Hall resistance and resistivity are
used synonymously. The longitudinal resistivity ρxx however, has a geo-
metrical factor, though, in the absence of scattering ρxx = 0. Thus in the
classical Hall effect, a plot of the Hall resistivity against the magnetic field is
a straight-line of unit slope, as shown in Fig. 3. The non-zero value of ρxx
is due to the finite life time of scattering.

ρ
xy
resistivity

ρ
xx

Magnetic Field B

Figure 3: Variation of Hall resistivity as a function of the magnetic field

strength - classical case

13
7.1 Integral Quantum Hall Effect
Before discussing the Quantum version of Hall effect, we will briefly recollect
some defining relations on resistivity. For a sample in two dimensions, the
conductivity tensor σ is defined by the following relations
jx = σxx Ex + σxy Ey
jy = σyx Ex + σyy Ey
Symmetry properties under time reversal requires σyx = −σxy . We may
also assume, by symmetry, σxx = σyy . The resistivity matrix is obtained by
inverting the matrix for the conductivity
 
1 σxx −σxy
ρ= 2 2
σxx + σxy σxy σxx
Thus
σxx
ρxx = 2 2
σxx
+ σxy
σxy
ρxy =− 2 2
σxx + σxy
Thus though it seems counter intuitive, if σxy 6= 0, then σxx = 0 implies
ρxx = 0, which implies perfect conductivity.
In 1980, K. von Klitzing1 found some interesting new facts about Hall
effect for high magnetic fields. He found that at liquid He temperatures and
at very high magnetic fields (typically ∼ 15 T or more), the Hall resistivity
ρxy does not change for a range of magnetic field strength, and jumps to the
next plateau as the range changes (see Fig. 4). On this plateau, the Hall
resistivity takes the values
h
ρH = ρxy = (34)
νe2
h
where ν is an integer, 1, 2, 3, . . .. The quantity 2 may be thought of as
e
the quantum of resistivity. Klitzing’s suggested this as an experiment for
accurate determination of the fine structure constant e2 /c~. This is known
as the Integer Quantum Hall Effect (IQHE). Klitzing was awarded the Nobel
prize in 1985 for this discovery.
1
K. v. Klitzing, G. Dorda and M. Pepper, Phys. Rev. Letters, 45, 494 (1980)

14
 4

3 ρ
xy
resistivity

R (h/e )
2 ρ

H
xx
1/2

2
1 1/3
1/4
1/5
1/6
0 5 B in Tesla 10 15

Figure 4: Variation of Hall resistivity as a function of the magnetic field

strength - quantum case

Subsequently, Tsui and Störmer also discovered what is known as the

Fractional Quantum Hall Effect where, instead of the integer ν in Eqn. (34)
for the Hall resistivity, one has a fraction f which can take various values,
the most common of which happen to be 1/3 and 2/3.

7.2 Landau Levels and IQHE

A somewhat simplified explanation of the integral quantum Hall effect is
based on considering the system of a two dimensional electron gas (2DEG) in
a strong magnetic field. The discussion requires an understanding of Landau
level degeneracies and the role of chemical potential (at low temperatures,
this is also the Fermi energy of the system). The chemical potential is defined
by
∂F
µ=
∂N
where F is the free energy of the system as a function of the number of
electrons N . Thus it is the change in the free energy of the system when
we add an additional electron to the system. In metallic solids, the energy
available to electrons are very close together; consequently the Fermi energy
is also the energy of the highest occupied level. Clearly, if there is a gap in
the energy levels, when the lower levels (or band in a solid) gets completely
full, the Fermi energy would jump to the higher level as one would require
higher energy to fill up such a level. This is what happens in our system

15
under discussion.
We had seen in (33) that the classical Hall resistivity is given by the expres-
B
sion ρH = , where we have replaced the charge q by the electronic charge
nec
e. If the electron density n is taken to be a value at which ν Landau levels
are filled, then, recalling that the degeneracy of a Landau level per unit area
Be
is given by (see Eqn. (30)) and the fact that each Landau level has the
ch
same degeneracy, , corresponding to a charge density for which exactly ν
Beν
states are filled, the charge density is given by n = . Substituting this
ch
into the expression for the Hall resistivity, we get
h
ρxy = (35)
νe2
When ρxy takes its non-zero constant value on a plateau, ρxx = 0 as well as
σxx = 0. The latter condition implies that no current flows in the longitudinal
direction while the former implies that it behaves like a perfect conductor
with no dissipation of energy. One can understand this result as follows.
When a certain number of Landau levels are just getting filled, there occurs
an energy gap ~ωc in the spectrum. Since the thermal energy kB T  ~ωc ,
the electrons in these levels cannot move to another level in the presence of a
small electric field. This implies ρxx = 0 at the edge of a plateau. However,
this does not explain why ρxx = 0 even when the Landau levels are only
partially full and the electrons are sitting on a plateau. This is explained
on the basis of the existence of disorder in the system which gives rise to
localized states instead of extended states. However, a discussion of this an
other subtle points of the theory is not within the scope of our course.

16
 Quantum Mechanics - I
Lecture-19
EPR and Bell’s Inequalities
Dipan Kumar Ghosh
Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
May 15, 2020

1 Introduction
In 1935 Einstein along with his coworkers Podolsky and Rosen 1 came out
with a thought experiment which suggests that the Copenhagen interpreta-
tion of quantum mechanics cannot provide a complete description of physical
reality. This classic paper came to be known as EPR paradox, after the ini-
tials of the three workers. They suggested taking a composite system of two
particles, with particle number 1, having a position x1 and momentum p1
and the particle number 2 having position x2 and momentum p2 . Note that
the position and momentum of a particular particle do not commute and we
have [qk , pk ] = i~δi,k . Thus the relative position x2 − x1 and the the total
momentum p1 + p2 of the particles commute as a result of which it is possible
to construct an eigenstate of these observables.
Suppose the system of particle has zero momentum, i.e. p1 + p2 = 0 and the
distance between them is large enough so that it may be assumed that any
measurement on one particle has no influence on the other. Einstein et. al.
did not specify how such a system may come to exist. However, one could
1
Einstein, A., B. Podolsky, and N. Rosen, 1935, “Can quantum-mechanical descrip-
tion of physical reality be considered complete?”, Physical Review, 47, 777-780 [available
online]

1
think of the system as that of an unstable particle which is initially at rest
but later disintegrates into two particles of equal masses. The process of
disintegration being an internal process, it would conserve momentum. Thus
it is possible to construct a simultaneous eigenstate of x2 − x1 and p1 + p2 .

(x2 − x1 )ψ = x0 ψ
(p2 + p1 )ψ = 0

Thus the pair of particles gets “entangled”. What it means is not possible to
describe state of one of the constituents independently of that of the other.
Later in this lecture we will provide a formal definition of entanglement.
Suppose after the particles have been widely separated, we measure the mo-
mentum of particle 1 and find it to be ~k, then the momentum of the second
particle becomes −~k and it would remain so in future. Suppose now we
measure the position of the first particle. This measurement cannot disturb
the momentum of the second particle but would fix the position of the sec-
ond particle. Thus at the end of the second measurement, we would have
precise information about both the position and momentum of particle 2,
violating Heisenberg’s uncertainty principle, which is one of the cornerstone
of Copenhagen interpretation.
Note that if we take the initial separation between the particles to be ac-
curately known, the relative momentum becomes uncertain, which in turn,
would make the separation between the particles uncertain as it changes with
time as (p2 − p1 )t/m.

2 Bohm’s Formulation of EPR Paradox

We will look at a different formulation of EPR paradox due to David Bohm,
who in 1951, gave the example of a spin zero system whose state is given by
1
ψ = √ (|↑↓i− |↓↑i)
2
This composite system decays into two spin 1/2 particles and in time move
far apart. Since the angular momentum is conserved, this pair of particles
would still have a total spin zero, irrespective of how far they may move away
from each other. Let us assume that Alice has particle 1 and Bob particle 2.
Suppose Alice makes a measurement of the z-component of the spin of the

2
particle in her possession. She will find Sz = ±~/2. Alternatively, using the
Pauli spin matrices, the value of σz will turn out to be either +1 or −1. In the
former case σz for Bob’s particle would be −1 and in the latter case it would
be +1, i.e. their values are anti-correlated. This is understandable because
the particles had interacted in the past and hence their z-components are
strongly correlated. However, at this stage if Alice makes a measurement of
the x-component of the spin of her particle. The z-component will no longer
have a fixed value but the x-component will be ±~/2 with equal probability.
Since the total angular momentum is zero, the x-component of the spin of the
particle number 2 will be respectively ∓~/2. However, since the particles are
far apart, how can the measurement of x-component of the spin of particle
number 1, affect the value of the spin of particle number 2? If it does not,
we conclude that both the x and the z component of the spin of particle
number 2 had definite value. How can that be true because [Sz , Sx ] 6= 0?
The way to reconcile these with quantum mechanics is to assume that the
particles remain entangled even though they might be separated by space-
like distances. Thus the first measurement makes the two particles to have
definite z- component of spin while the second measurement makes the z-
component fuzzy but gives a definite value to the x-component. The question
then arises as to whether it violates the principle of relativity? It does not
because Bob has no way of knowing (without making a measurement) that
the particle with him has a definite x-component now. If he does indeed
measure it, he still has no way of knowing that it was due to Alice had made
a measurement making the state of his particle collapse to a particular state.
Consider what would happen if after Alice made a measurement and got σz =
+1, Bob makes a measurement but instead of measuring the z-component of
the spin measures along an arbitrary direction (sin θ cos ϕ, sin θ sin ϕ, cos θ),
which makes an angle θ with the z-axis and has an azimuthal angle ϕ with the
x-axis. The eigenstates of Pauli vector along the n̂ direction corresponding
to eigenvalues ±1 are given by
 
cos(θ/2)
| n̂, +1i = iϕ (1)
e sin(θ/2)
 
sin(θ/2)
| n̂, −1i = (2)
−eiϕ cos(θ/2)
Thus the state | ẑ, −1i is given by
| ẑ, −1i = sin(θ/2) | n̂, +1i − cos(θ/2) | n̂, −1i

3
Thus the measurements are still correlated, though there is no perfect anti-
correlation as in the previous case.
Let us look at the situation in terms of the rival points of view. According
to quantum mechanics, a system does not have property independent of
observation and it is the process of measurement which reveals the value
of a physical observable based on some probabilities. The “hidden variable
theory” would suggest that the value of the physical observable was coded
into some variables hidden from our eyes and it is the process of measurement
which reveals what was not apparent in the theory. Since these variables are
not apparent in our description of the system, they are termed as hidden
variables.

3 Entanglement
Loosely speaking, entanglement is a feature of a well separated but a compos-
ite system where there exists a correlation between results of measurement
on different parts of the system. Such correlations exist even when the parts
are widely separated. This has led to the term “spooky action at a distance”
to describe such behaviour. When a system is entangled, the individual parts
of the system are linked together as a single entity so that when we make
a measurement on a part, we really make the measurement on the system
itself.
Consider all states belonging to the space HA ⊗HB . Using two particle basis,
a state in the system may be written as | ψi = α | 00i + β | 01i + γ | 10i + δ |
11i. A non-entangled state may be expressed as a product of a state in HA
and another in HB , i.e. as

(a | 0i + b | 1i) ⊗ (c | 0i + d | 1i) = ac | 00i + ad | 01i + bc | 10i + bd | 11i (3)

It may be seen that the product of coefficients of states | 00i and | 11i is
equal to that of the product of the coefficients of | 01i and | 10i. Thus the
state | ψi of (3) can be written as product of two single particle states and
hence non-entangled if
αδ = βγ (4)
In an experimental set up involving photons, we consider a source emitting
two photons which go in different directions are are received by Alice and Bob
(Figure 1). The arrangement is very similar to Bohm’s description of a spin

4
 Alice Bob

γ Ψ γ

Two Photon Source

Figure 1: Decay of a singlet particle into two photons

zero particle decaying into two spin half particles except that in the present
case we use photons instead of spins. The measurement that is done by Alice
and Bob is to measure the state of polarization of the photon received by
them, which could be either horizontal (H) or vertical (V ). Alice measures
the state of polarization by using a polarizer whose pass axis makes an angle
α with the horizontal while Bob does the same but in his case the axis of
polarizer makes an angle β with the horizontal. If they look at their results
individually, they would find that there is an equal probability of the photon
received by each having a polarization along the axis or perpendicular to it
and it does not depend on the angle that the axis of the polarizer makes.
This shows that the measurement of each is local and is not influenced by
the other observer.
The basis used by Alice is taken to be
| α, ki = cos α | Hi + sin α | V i
| α, ⊥i = sin α | Hi − cos α | V i
and that used by Bob is
| β, ki = cos β | Hi + sin β | V i
| β, ⊥i = sin β | Hi − cos β | V i
However, if Alice and Bob are to compare their notes after the measurements
they would find that the results of their measurements are correlated. Note
that there are four possible results of the measurements (i) Alice and Bob
both get k, (ii) they both get ⊥, (iii) Alice gets k but Bob gets ⊥ and (iv)
Alice gets ⊥ but Bob gets k. For ease of notation, we would denote k as +
and ⊥ as −. Since the state ψ leads to a singlet state of two photons, we
take the state ψ as
1
ψ = √ (| Hi | V i− | V i | Hi)
2

5
Thus the probability amplitude of Alice and Bob getting identical result, viz.
| ++i or | −−i is given by
1
hψ | ++i = √ [hH | hV | −hV | hH |] [(cos α | Hi + sin α | V i)(cos β | Hi + sin β | V i)]
2
1 1
= √ [cos α sin β − sin α cos β] = √ sin(β − α)
2 2
Similarly the probability amplitude of getting unequal results | +, −i or
| −, +i is given by
1
hψ | +−i = √ [hH | hV | −hV | hH |] [(cos α | Hi + sin α | V i)(sin β | Hi − cos β | V i)]
2
1 1
= √ [− cos α cos β − sin α sin β = √ cos(α − β)
2 2
The probability is given by the square of the above expressions, which are
given by
1 1
P (+, +) = P (−, −) = ( sin2 (β − α))2 = [1 − cos 2(β − α)]
2 4
1 2 2 1
P (+, −) = P (−, +) = ( cos (β − α)) = [1 + cos 2(β − α)]
2 4
The probability of outcome depends on the bases that Alice and Bob used for
their measurements. Note that these correlations do not depend on how far
apart Alice and Bob are nor on the time elapsed between the measurement
by the two. The problem with quantum mechanics is that though it provides
an estimate of these probabilities it does not explain how two measurements
which are spatially and temporally apart could be correlated like this. Ein-
stein et. al. perceive this to be a failure of standard interpretation of
quantum mechanics and suggest that such correlation arise because of values
taken by the hidden variables at the time of creation of the two photons. We
will see later that quantum mechanics does not provide a mechanism because
there is none that exists.

4 Bell’s Inequalities
The above discussion generated two rival points of view which may be sum-
marised as follows:

6
 1. Quantum Mechanics : A system does not have properties indepen-
dent of observation, quantum mechanics merely gives probabilities with
which certain results may occur if an observable is measured.
2. Local Hidden Variables : The property of the system, though revealed
during a measurement was pre-ordained as it was encoded in some
hidden variables of the system.
John Bell in 1964 suggested a gedanken experiment with the aim of settling
this argument. There have been many variations of his original argument
all having the same philosophy. The idea is to assume that there exist some
hidden variables and then proceed to obtain certain constraints that such as-
sumption lead us to which are in direct conflict with what would be predicted
by quantum mechanics. The validity of one theory or the other could then
be tested by doing actual experiments to test such conflicting conclusions.
There have been several versions of Bell’s inequalities, all essentially with the
same central theme. We will consider a couple of these.

Consider the production of a pair of spin 1/2 particles from a composite

system which is a singlet. By conservation of angular momentum we know
that if Alice measures σz for her particle and finds it to be +1, Bob would
find σz = −1 for his particle. (In an optical experiment, we could consider
production of a pair of photons as discussed before. There is a definite cor-
relation between the polarization of the emitted photons because parity is
conserved in atomic processes. The argument is very similar to the case of
spin, which we talk in the following.)

Alice and Bob randomly choose which of the three directions, x, y or

z they want to measure the spin component. We will omit ~/2 factor and
mention only the value of the component of Pauli vector ~σ . The choice of
the axis of measurement is absolutely arbitrary. However, we assume local
realism, i.e. the value that is revealed in the experiment is the value that
is an intrinsic property of the particle and not any probabilistic value. The
other fact assumed is that at the time of creation, a given component of σ
of the two particles have opposite values, i.e. if Alice measures σi = +1 for
her particle, Bob would measure −1 for his particle. Thus in the following
thought experiment we would only consider those events where Alice and
Bob randomly pick unequal axes. This would give simultaneously give us
the values of two different components of σ, something which the quantum

7
mechanics would not allow us to presume. The following table gives us the
possible values of σx , σy and σz . For brevity, we have used ± in place of ±1.
The table only gives us the possible values of Alice’s particle. Bob would get
just the complementary value when he chooses the same axis.
Event Group σx σy σz
N1 + + +
N2 + + − (B C̄ and AC̄)
N3 + − + (AB̄)
N4 + − − (AB̄ and AC̄)
N5 − + +
N6 − + − (B C̄)
N7 − − +
N8 − − −
The events have been grouped in eight event classes N1 to N8 . The
principle of Bell’s inequality is the following. Suppose we could perform
three different measurements on a particle, each measurement can give us
one of the two answers +1 or −1, like in a true/false question. Let us call
these tests A, B and C. In the present case the tests consist of measuring the
σx , σy and σz of Alice’s particle. If N (A, B̄) represents the number of events
in which A = + and B = −, N (B, C̄) represents the number of events in
which B = + and C = − and N (A, C̄) represents the number of events in
which A = + and C = −, then

N (A, B̄) + N (B, C̄) ≥ N (A, C̄)

This may be easily seen from the above table in which it can be seen that
the number of events for which (A, C̄) cannot increase without increasing
N (A, B̄) and N (B, C̄). A simpler proof is seen by considering the Venn
diagram representation of the events. It may be seen that the region AB̄
is given by sum of the regions indicated by A1 and AC, the region B C̄ is
given by sum of the regions B1 and AB and the region AC̄ is given by
A1 + AB. The shades region in the figure lies within all three.Thus the last
region lies completely within the sum of the first two regions, proving the
inequality. The number of times an event occurs in a sample of large number
of experiments is a measure of the probability of that event. Dividing the
above equation by the total number of events we get Bell’s inequality

P (A, B̄) + P (B, C̄) ≥ P (A, C̄) (5)

8
 B1

AB
A1
BC
AC
C1

Figure 2: The events AC̄ completely lies within the region (AB̄) ∪ (B C̄)

Consider for example a particular sample, say N2 which, for Alice gives
the values +, +, − for σx , σy and σz respectively. If Alice and Bob measure
different components of σ for events in this group, their results will be as
follows :
Alice’s Axis Bob’s Axis Alice’s value Bob’s value

X Y + − dissimilar
X Z + +
Y X + − dissimilar
Y Z + +
Z X − −
Z Y − −
It may be seen that Alice and Bob get dissimilar results (i.e, if Alice gets
+, Bob gets − and vice versa) only in 2 out of 6 cases, i.e. in one third
of the cases. In particular, in any population such dissimilar results would
arise in at least one third of cases. Remember these conclusions are obtained
assuming local realism without bringing quantum mechanics into the picture.
We will see what happens to the scenario in quantum mechanics.

5 The Quantum Picture

Let us consider a spin zero pair shared by Alice and Bob. Alice has particle
1 and Bob has particle 2. We take the quantisation axis to be the z-axis, so

9
that the wavefunction of the pair is written as
1
| ψi = √ (| 0i | 1i− | 1i | 0i)
2
   
1 0
where the basis is taken as | 0i = and | 1i = , corresponding to the
0 1
eigenvalues ±1 for σz . We consider three non-orthogonal axes, Â, B̂ and Ĉ
as shown in the figure. We take  to be the ẑ axis itself, B̂ to make an angle
θ with the  axis and Ĉ to make an angle θ with the axis B̂, i.e. an angle
2θ with Â.
^
A ^
B
^
C

θ
θ

Figure 3: Axes chosen by Alice to measure the component of spin

We will now calculate the probability P (A, B̄), i.e. Alice measures along
axis  and gets +1 as eigenvalue of σA and she gets −1 as eigenvalue when she
measures the spin component along B̂. However, since the second particle
belongs to Bob, it implies that Bob, measuring along the axis B̂ gets the
eigenvalue to be +1. The probability is calculated as follows :

P (A, B̄) = |hψ | | 0i ⊗ (cos(θ/2) | 0i + eiϕ sin(θ/2) | 1i) |2

 

1
= | [h0 | h1 | −h1 | h0 |] | 0i ⊗ (cos(θ/2) | 0i + eiϕ sin(θ/2) | 1i) |2
 
2
1
= sin2 (θ/2)
2
Since the angle between the axes A and C is 2θ by a similar argument,
1
P (A, C̄) = sin2 (θ)
2
10
 We need to calculate P (B, C̄). This is given by taking the projection of
the state | ψi along the axis B with Alice and Bob’s bases along C.

P (B, C̄) = |hψ | (cos(θ/2) | 0i + eiϕ sin(θ/2) | 1i) ⊗ (cos(θ) | 0i + eiϕ sin(θ) | 1i) |2
 

1
= | [h0 | h1 | −h1 | h0 |] eiϕ cos(θ/2) sin(θ) | 0i | 1i + eiϕ (sin(θ/2) cos(θ) | 1i | 0i |2
 
2
1 1
= sin2 (θ − θ/2) = sin2 (θ/2)
2 2
In order to satisfy Bell’s inequality, we must have

P (A, B̄) + P (B, C̄) ≥ P (A, C̄)

i.e.
sin2 (θ/2) + sin2 (θ/2) ≥ sin2 (θ)
As there is no restriction on our choice of the axes, we may choose θ = π/4,
which requires

2 sin2 (π/8) ≥ sin2 (π/2) =⇒ 1 − cos(π/4) ≥ cos(π/4)

√
i.e. 1 ≥ 2. Thus quantum mechanical laws would violate Bell’s inequality,
providing a test for its validity.

6 CHSH Inequality
There are many variations of Bell’s inequalities. One such inequality is known
as CHSH inequality after Clauser, Horne, Simone and Holt2 . We start with
1
a collection of large number of singlet states √ (| 01i− | 10i), with the first
2
particle being with Alice and the second with Bob. As there are multiple
identical copies they may make several measurements and make statistical
inferences. Alice can measure two observables Q and R while Bob can mea-
sure two others S and T . Each of these variables can take two values ±1.
A non-quantum mechanical example of such variables is the following. We
assume that Alice and Bob have a collection of T-shirts which come in two
sizes, large (L) and medium(M), have two different colors, red (R) and blue
(B), two different neck types, polo or V neck and two different price tags.
2
http://www.theory.caltech.edu/ preskill/ph229/notes/chap4.01.pdf

11
Alice can measure two properties, say, size and price and Bob two others,
i.e. color and neck type. Since each of the properties take binary value,
they make a note of the properties and prepare a table. in deriving CHSH
inequality, we assume that each property is inherent to the T-shirt and does
not depend on the observation itself.
Let us look at the value of the expression C = QS + RS + RT − QT which
is obtained from a group of 4 random observations. We have

C = QS + RS + RT − QT = (Q + R)S + (R − Q)T

Since each of the variables take ±1 value, either Q + R or Q − R is zero.

When one of the terms is zero, the other term takes value ±2. Thus the
average value is given by

| hCi |≤ h| C |i = 2

Hence
|hQSi + hRSi + hRT i − hQT i| ≤ 2 (6)
This, essentially is CHSH inequality which is derived by assuming that the
result of observations are because of inherent values of the variables and not
because of the process of observation. We will now examine what happens
in quantum mechanical processes. Let us define 4 observables which take
binary values, i.e. their eigenvalues are ±1.
A
Q = σm , R = σnA , B
S = σm , T = σkA

where the superscripts A and B represent Alice and Bob and the subscripts
are the four directions in which the components of the Pauli matrix are to
A B
be taken. Let us evaluate hσm σm i. 3
Let the direction m̂ = (θm , ϕm ) and k̂ = (θk , ϕk ). We have

sin θm e−iϕm
 
cos θm
σm =
sin θm eiϕm − cos θm
It follows
   
1 cos θm
σm | 0i = σm = = cos θm | 0i + sin θm eiϕm | 1i
0 sin θm eiϕm
3
A much simpler proof using the density matrix formulation is given in the box

12
and
sin θm e−iϕm
   
0
σm | 1i = σm = = sin θm e−iϕm | 0i − cos θm | 1i
1 − cos θm

which gives
A
σm | 0iσkB | 1i = (cos θm | 0i + sin θm eiϕm | 1i)(sin θk e−iϕk | 0i − cos θk | 1i)
= cos θm sin θk e−iϕk | 00i − cos θm cos θk | 01i
+ sin θm sin θk ei(ϕm −ϕk ) | 10i − sin θm eiϕm cos θk | 11i
A
σm | 1iσkB | 0i = (sin θm e−iϕm | 0i − cos θm | 1i)(cos θk | 0i + sin θk eiϕk | 1i)
= sin θm e−iϕm cos θk | 00i + sin θm sin θk e−i(ϕm −ϕk ) | 01i
− cos θm cos θk | 10i − cos θm sin θk eiϕk | 11i

Thus
A B 1 A B
σm σk | ψi = √ σm σk (| 01i− | 10i)
2
1 
= √ (cos θm sin θk e−iϕk − sin θm e−iϕm cos θk ) | 00i
2
+ (− cos θm cos θk − sin θm sin θk e−i(ϕm −ϕk ) ) | 01i
+ (sin θm sin θk ei(ϕm −ϕk ) + cos θm cos θk ) | 10i
−(sin θm eiϕm cos θk + cos θm cos θk | 10i − cos θm sin θk eiϕk ) | 11i


Thus
1
A B
−2 cos(θm − θk ) − sin θm sin θk e−i(ϕm −ϕk ) − sin θm sin θk ei(ϕm −ϕk )

hψ | σm σk | ψi =
2
= − cos(θm − θk ) − sin θm sin θk cos(ϕm − ϕk ) = −m̂ · k̂

The last identity follows because

m̂ · k̂ = sin θm cos ϕm sin θk cos ϕk + sin θm sin ϕm sin θk sin ϕk + cos θm cos θk
= sin θm sin θk cos(ϕm − ϕk ) + cos θm cos θk

13
 The above relation can be easily es-
tablished using the density matrix
formulation.Using the perfect anti-
correlation between Alice’s and Bob’s ^ Alice
m
measurements when using the same ^k Bob

axis, we have
A B A A
hψ | σm σk | ψi = −hψ | σm σk | ψi
π/4
. Thus we have π/4 ^
n Alice
π/4
σk | ψi = −hψ | (~σ A · m̂)(~σ A · ˆl) | ψi
A A
−hψ | σm
X
=− mi kj Tr (ρA σiA σjA )
ij
X
=− mi kk Tr (ρA δij )
Bob ^
ij l
X Figure 4: Axes used by Alice and Bob
=− mi ki = −m̂ · k̂
i
in CHSS measurements

the last relation follows because

Tr (ρA ) = 1.
Consider the case where m̂, k̂, n̂ and ˆl all lie in one plane and are spaced by
π/4 from one the preceding one. We then have

A B 1
hQSi = hσm σk i = − cos(π/4) = − √
2
1
hRSi = hσnA σkB i = − cos(π/4) = − √
2
1
hRT i = hσnA σlB i = − cos(π/4) = − √
2
A B 1
hQT i = hσm σl i = − cos(3π/4) = √
2
We then require
1 √
√ =2 2≤2
2
showing that quantum mechanics would violate CHSS inequality.

14
7 Experimental Verification of Validity of Quan-
tum Mechanics
4

In 1992, Aspect et. al. provided experimental verification of the pre-

dictions of quantum mechanics. The experiment consisted of measuring the
polarization correlation of visible photons ( ν1 = 551.3 nm and ν2 = 422.7
nm) emitted in J = 0 to J = 1 to J = 0 calcium atomic cascade. Pumping
is done by a two photon absorption process using blue laser.
Upper level

ν = 551.3 nm
1

ν = 422.7 nm
2
Ground level

[Figure 5 : Atomic cascade used in producing entangled photons in As-

pect experiment] The fluorescent light collected by two large aperture lenses
and made incident on two polarizers, which could be placed along arbitrary
directions â and b̂ in the x-y plane, which is perpendicular to the direction
of propagation of light. In the figure shown (Figure 6) they are both shown
along the x-axis. Each polarizer has two channels, to detect each type of
polarization. Thus, if the light coming from the polarizer A is polarized par-
allel to the axis, it will emerge from the output channel marked +1. If, on
the other hand, the polarization is perpendicular to the axis, it will emerge
from the channel −1.
4
A. Aspect, J. Dalibard, and G. Roger, “Experimental Test of Bell’s Inequalities Using
Time -Varying Analyzers,” Phys. Rev. Lett. 49, 1804 (1982).

15
 [Figure 6: Schematic diagram of Alain Aspect experiment (source : web
archives)]
The second photon having a frequency ν2 falls on the polarizer along the
b− axis. Once again if the polarization direction is parallel to the axis, it
would emerge from channel +1 of the second polarizer and if perpendicular,
it would emerge from channel −1.
For the entangled photon state | ψi, quantum mechanics predicts the po-
larization to be random, being parallel 50% of the time and perpendicular
the other 50%. However, quantum mechanics presdicts a strong correlation
between the polarization of the pair of photons. For both â and b̂ along
the x− axis, the polarization state of both photons should be the same, i.e.,
+1, +1 or −1, −1 but never +1, −1 or −1, +1. One can determine the four
coincidence rates and check for the validity of Bell’s inequalities. Local real-
ism theory bestows some correlation between them but such correlations are
limited. In making the measurements, the polarizer settings are switched at
ultra fast rate so that the setting changes when the two photons are in flight,
travelling about 100 m in some experiments. This stops the photons from
receiving communication from each other’s state.
The result of such experiments confirm quantum hypothesis by providing
direct proof of violation of Bell’s inequalities.

16
8 Entanglement and Bell’s Inequalities
As Bell’s inequality is derived under the assumption of the existence of hidden
variables, no violation of the inequality would occur in quantum states which
are separable. This is because correlations that might exist between sub-
systems are classical in nature. Consider, on the other hand, an entangled
state such as
| ψi = α | 00i + β | 11i
1
The maximally entangles state corresponds to α = β = √ . Suppose Alice
2
and Bob measure their observables a and b in the x-z plane.

a = σzA cos θA + σxA sin θA

b = σzB cos θB + σxB sin θB

We have

hψ | σzA ⊗ σzB | ψi = (α∗ h00 | +β ∗ h11 |) (α | 00i + β11)

=| α |2 + | β |2 = 1
hψ | σxA ⊗ σxB | ψi = (α∗ h00 | +β ∗ h11 |) (α | 11i + β | 00i)
= α∗ β + β ∗ α
hψ | σzA ⊗ σxB | ψi = (α∗ h00 | +β ∗ h11 |) (α | 01i − β | 10i)
= 0 ≡ hψ | σxA ⊗ σzB | ψi

Thus

habi = hψ | ab | ψi
= cos θA cos θB + (αβ ∗ + βα∗ ) sin θA sin θB

1
For the maximally entangled state we have, substituting α = β = √
2
habi = cos θA cos θB

17
 Alice a^ ^b
Bob Bob
^
b’

−θ
θ

^
a’ Alice

[Figure 7 : Axes used by Alice and Bob]

Consider CHSS expression habi + ha0 bi + hab0 i − ha0 b0 i. Take the axes of
measurement of Alice and Bob as shown in Figure 7 : θa = 0, θa0 = π/2, θb = θ
and θb0 = −θ. We get

habi+ha0 bi+hab0 i−ha0 b0 i = cos θ+(α∗ β+β ∗ α) sin θ+cos θ+(α∗ β+β ∗ α) sin θ ≤ 2

i.e.
cos θ + (α∗ β + β ∗ α) sin θ ≤ 1
Taking θ ' 0 the above inequality may be made to be violated. This shows
that violation of Bell’s inequality is a consequence of entanglement and vice
versa.

18
 Quantum Information and Computing- II
Density Matrix Formulation of Quantum
Mechanics
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
April 22, 2016

1 Introduction
Earlier, we have discussed the postulates of quantum mechanics. However, under many
situations, we find these axioms to be violated. This happens because most of the time,
the system that we wish to study, is a part of a much larger system. In such a case, it is
found that (i) the states may not be represented by rays in their own Hilbert space, (ii)
measurements may not be orthogonal projections and the evolution may not be unitary.
To illustrate this consider the following two examples:
Consider a two dimensional Hilbert space with basis vectors {| xi, | yi}. Suppose we
prepare a large number of such systems, where each of the members is prepared in one of
the two states,

| ai = α | xi + β | yi
| bi = γ | xi + δ | yi (1)

where | α |2 + | β |2 =| γ |2 + | δ |2 = 1. Thus, if we select a system in state | ai and make

a measurement in the basis {| xi, | yi}, we would get the state | xi with a probability
| α |2 and likewise for the result | yi.
Suppose now, that out of the N systems prepared by us na systems are in the state | ai
and nb number of the systems are in the state | bi, such that na + nb = N . If we pick a
random system from this ensemble of N systems, the probability that the selected system
is in the state | ai has a probability pa = na /N and the probability it it has the state
| bi has a probability nb /N = 1 − p. These probabilities are just the classical probability
which works at the ensemble level. However, once the system is selected, the measurement
probabilities are determined by Born interpretation of quantum mechanics. This is an
c D. K. Ghosh, IIT Bombay 2

example of an open system in which we need to modify our rules of quantum mechanise,
as discussed earlier.
Consider a second example. Suppose we call our system of interest as system A which
interacts with its environment, which we call as system B. If the state of the combined
system factorises into a product of a state of system A with that of system B,i.e. if
| ψAB i =| ψA i⊗ | ψB i
the effect of the environment can be neglected because given any operator OA , which
only acts on the system A but not on B, we have
hψAB |OA | ψAB i = hψA |OA | ψA i
In such a situation, the system A is said to be in a pure state. However, if the state of
system of interest is not disentangled from the environment, the effect of the environment
cannot be factored out. The word “environment” need not be a big system, one could
consider a two bit system, with one of the qubits belonging to the Hilbert space HA and
the other (the “environment”) belonging to the Hilbert space HB . Consider a state in the
composite space HA ⊗ HB ,
| ψi = a | 0iA ⊗ | 0iB + b | 1iA ⊗ | 1iB
Note that the qubits A and B are correlated in that when we measure the qubit A, we
would project it to {| 0i, | 1i} basis of system A. The probability with which we will find
it is state | 0i is | a |2 . In this case, the state would collapse to | 0iA ⊗ | 0iB . Note that
the system B is in a definite state. Same is true of the measurement | 1iA . The system
A is said to be in a mixed state. In dealing with mixed state (as also with pure state)
a more appropriate formalism is provided by Density Matrix.

2 Density Matrix
Let us look at a general measurement of the system A irrespective of its effect on B. Such
a measurement operator is MA ⊗ IB . We then have,

AB hψ |MA ⊗ IB | ψiAB = [a∗ A h0 | ⊗ B h0 | + b∗ A h1 | ⊗ B h1 |(MA ⊗ IB )[a | 0iA ⊗ | 0iB + b | 1iA ⊗ | 1iB

=| a |2 A h0 |MA | 0iA + | b |2 A h1 |MA | 1iA
= hMA i = tr(MA ρA ) (2)
where the operator ρA is the density operator or the density matrix,
ρA =| a |2 | 0iA A h0 |+ | b |2 | 1iB B h1 |
and the operator MA acts on qubit A only. We can interpret ρA as an ensemble of
possible quantum states each of which occur with a specified probability, P0 =| a |2 , Pa =|
b |2 . Thus, in the above, we have talked about two distinct type of states:
c D. K. Ghosh, IIT Bombay 3

1. A coherent superposition of states | 0iA and | 1iA

2. a probabilistic superposition in which the states | 0i and | 1i occur with a predeter-

mined and specified probability.

To see the distinction consider measurement of σx in these two types of states. Consider a
1
coherent superposition √ (| 0i+ | 1i). The expectation value of σx in this state is given
2
by
1
hσx i = (h0 | +h1 |) X (| 0i+ | 1i)
2
1
= (h0 | +h1 |) [| 0ih1 | + | 1ih0 |] (| 0i+ | 1i)
2
1
= (h0 | +h1 |) (h1 | +h0 |)
2
=1

On the other hand, if we consider an ensemble in which the state | 0i and | 1i occur
1
with a probability of 1/2 each, we get hσx i = (hα |X| αi + hβ |X| αi) = 0. In this case
2
the density matrix is
1 I
ρ = (| αihα | + | βihβ |) =
2 2
so that
1
hσx i = tr(σx ρ) = tr(σx ) = 0
2
Thus the density operator is an average operator which allows us to describe a system
which is not necessarily in a pure state but may be a statistical mixture of pure states. we
first start with the case where the system is in a pure state. Let {| ei i} be a basis in the
P
Hilbert space of the system in terms of which the state | ψi is given by | ψi = i ci | ei i.
Note that this is not a mixture but is a pure state. The expectation value of an operator
 in this state is given by
X
hAi = hψ |Â| ψi = c∗i cj Ai,j
i,j

where Ai,j = hei |Â| ej i, cj = hej |ψi and c∗i = hψ |ei i. We have

c∗i cj = hψ |ei ihej |ψi

= hej |ψihψ |ei i
= hej |(| ψihψ |)| ei i
= hej |ρ̂| ei i

where
ρ̂ =| ψihψ | (3)
c D. K. Ghosh, IIT Bombay 4

is the density matrix for the pure state, which is just the projection operator for the state
| ψi. In terms of the density matrix, the expectation value of  can be written as
X
hÂi = hej |ρ̂| ei iAi,j
i,j

. We can rewrite the above expectation value as follows:

X
hÂi = hej |ψihψ |ei ihei |Â| ej i
i,j
X
= hej |ρ̂| ei ihei |Â| ej i
i,j
X
= hej |ρ̂Â| ej i
j

= tr ρ̂Â (4)
In the last but one step, we have used the completeness relation to perform the sum over
i. Note that the trace of ρ̂ itself can be calculated as follows, since trace can be calculated
in any basis,
X X
tr ρ = hei |ρ̂| ei i = hei |ψihψ |ei i
i i
X X
= c∗i ci = | ci |2 = 1
i i

Example: r
1 2
A system is in the state | ψi = √ | e1 i + i | e2 i. Determine the density operator and
3 3
find its trace.
Solution:

ρ̂ =| ψihψ |
r ! r !
1 2 1 2
= √ | e1 i + i | e2 i √ he1 | −i he2 |
3 3 3 3
√
1 2 i√ 2
= | ei ihe1 | + | e2 ihe2 | − 2 | e1 ihe2 | +i | e2 ihe1 |
3 3 3 3
The trace is easy to calculate
1 2
tr ρ̂ = he1 |ρ̂| e2 i + he2 |ρ̂| e2 i = + = 1
3 3
How does the density operator evolve with time? As the state | ψi satisfies the
Schrödinger equation, we have
d
i~ | ψi = H | ψi (5a)
dt
d
−i~ hψ | = hψ | H (5b)
dt
c D. K. Ghosh, IIT Bombay 5

We thus have
   
d d
i~ | ψihψ | = i~ | ψi hψ | + | ψi i~ hψ |
dt dt
= H | ψihψ | − | ψihψ | H
= [H, ρ]

where we have use (??) and (??). Thus the density matrix satisfies Liouville equation,

d
i~ ρ̂ = [H, ρ̂] (6)
dt

Note that though ρ is an operator, it does not satisfy the quantum mechanical Heisen-
berg equation of motion. This is because the density operator does not represent any
observable and simply has the mathematical structure of an operator.
The density operator is clearly hermitian as ρ† =| ψihψ |. Further,

ˆ |= ρ
ρ2 = (| ψihψ |) (| ψihψ |) =| ψiIhψ

This is true of pure states only, for which we have,

tr ρ2 = tr ρ = 1

Not also that ρ is a positive operator, because for an arbitrary state | φi, we have

hφ |ρ| φi = hφ |ψihψ |φi =| hφ |ψi |2

Since ρ is self adjoint (hence normal) we can use a spectral decomposition for the operator
X
ρ= λn | nihn |
n

As ρ is a positive operator, the eigenvalues are nonnegative. This along with tr ρ = 1

P
gives n λn = 1,

3 Mixed State Density Matrix

If instead of a pure state, we have an ensemble in which systems could be in various states
| ψi with classical probability pi , we define the density operator by the relation
X X
ρ= pi ρi = pi | ψi ihψi | (7)
i i

The states | ψi i s need not be orthogonal.The properties of the density operator are as
follows:
c D. K. Ghosh, IIT Bombay 6

(i) ρ† = ρ

(ii) ρ is a positive operator

(iii) tr(ρ) = 1

(iv) hAi = tr(ρA)

d
(v) It satisfies Liouville equation i~ ρ = [H, ρ]
dt

3.1 Density Matrix and Bloch Sphere

Consider the density matrix corresponding to spin 1/2. Recall that a point on the Bloch
sphere is associated with the state of a qubit. Naturally, for every point on the Bloch
sphere, we can associate a density matrix as well. One can see it directly by considering
the eigenstates of σn , where the unit vector n̂ has coordinates (sin θ cos ϕ, sin θ sin ϕ, cos θ).
The eigenstates are given by  
θ
 cos 2 
| ψi =  θ
eiϕ sin
2
The corresponding density matrix can be calculated using ρ =| ψihψ |, so that

ρ =| ψihψ |
 
2 θ −iϕ θ θ
cos e sin cos 
=
 2 2 2
iϕ θ θ 2
e sin cos sin θ
2 2
cos θ e−iϕ sin θ
 
= iϕ
e sin θ − cos θ
     
1 1 0 1 1 0 −i 1 1 0
= I + sin θ cos ϕ + sin θ sin ϕ + cos θ
2 2 1 0 2 i 0 2 0 −1
1
= (1 + n̂ · ~σ )
2
It is possible to associate a density matrix for the mixed state with the Bloch sphere,
only that such points lie inside the sphere and not on it as is the case for the pure states.
Since any 2 × 2 matrix can be written in terms of a unit matrix and the three Pauli
matrices σx , σy and σz , we can write

1
ρ = (1 + ~a · ~σ )
2
c D. K. Ghosh, IIT Bombay 7

Since tr(σi ) = 0 and tr(I) = 2 for a 2 × 2 identity matrix, we have tr(ρ) = 1. the vector
~a is called the Bloch vector. Note that

σx = tr(σx ρ)
1
= tr (σx (1 + ax σx + ay σy + az σz ))
2
ax
= tr(σx2 )
2
ax
= × 2 = ax
2
In the above we have used the properties of the Pauli matrices such as σx σy = iσz , σi2 = I
and the fact that the trace of σi is zero. The above result shows that ax , ay and az are
respectively the expectation values of σx , σy and σz . Let us calculate the trace of ρ2 . We
have,
1
tr(ρ2 ) = tr[ (I + ~a · σ)2 ]
4
1
= tr[I 2 + a2x σx2 + a2y σy2 + a2z σz2 + 2ax σx + 2ay σy + 2a − zσz ]
4
1
= [1 + a2x + a2y + a2z ]
2
1+ | a |2
=
2
In the above, we have used tr(σi ) = 0 and tr(σi2 ) ≡ tr(I) = 2. Thus for mixed states, we
require the distance from the centre | a | to be less than 1 and hence they lie inside the
Bloch sphere.
1
What is the difference between a pure state | ψi = (| 0i+ | 1i) and a system which is
2
a statistical mixture of 50% in | 0i and another 50% in | 1i state? For the pure state,
the state | ψi is on the Bloch sphere with θ = π/2, ϕ = 0, because the state has a matrix
representation  π 
π cos( ) 1
ψ( , 0) =  i×0 4 π  = √ (| 0i+ | 1i)
2 e sin( ) 2
4
If we rotate this state on the Bloch sphere by −π/2 about the y-axis, the state would go
to the north pole, i.e. to the state | 0i. On measurement, we would get the state | 0i
with unit probability. Consider now what would happen if we had a mixture given above.
Rotating the Bloch sphere by −π/2 about the y-axis would take | 0i to the equator, to
1 1
the state √ (| 0i− | 1i). Similarly the state | 1i would go to (| 0i+ | 1i). Hence we
2 2
would, on measurement, get the state | 0i with 50% probability and the state | 1i with
50% probability, the same as was the case before rotation. The mixed state lies at the
origin of the Bloch sphere and hence does not change on rotation described above.
c D. K. Ghosh, IIT Bombay 8

Does density matrix uniquely represent a physical system? For a mixed system, the
answer is no. Consider the 50-50 mixture given above. The density matrix is
1 I
ρ = (| 0ih0 | + | 1ih1 |) =
2 2
1
Consider a different mixture consisting of 50% in the state | +i = (| 0i+ | 1i) and
2
1
another 50% in the state | −i = (| 0i− | 1i). The density matrix works out to be same
2
as in the previous case!
The elements of the density matrix are interpreted as follows. If a system is described
by a density matrix ρ, the probability of of finding it in a state | ψi is given by hPψ i,
where Pψ =| ψihψ | is the projection operator for the state | ψi. Consider a pure
state | ψi = a | 0i + b | 1i. The probability of finding this state in the state | 0i is
hψ |P0 | ψi =| a |2 . For an arbitrary state described by a density matrix,

P0 = tr(P0 ρ)
  
1 0 ρ00 ρ01
= tr
0 0 ρ10 ρ11
 
ρ ρ01 1 + az
= tr 00 = ρ00 =
0 0 2

Likewise, the probability to find it in state | 1i is given by

1 − az
P1 = ρ11 =
2
The probability of find the system in a certain state is given by the diagonal element of
the density matrix. The off-diagonal elements give the coherence between the states.
Note that for a pure state ρ2 = ρ. Using the spectral theorem, ρ = i λi | λi ihλi | in
P

which case ρ2 = i λ2i | λi ihλi |. Since ρ2 = ρ we have λ2i = λi , so that λi = 0 or 1 (ρ

P

being Hermitian λi are real). Since tr(ρ) = 1 we have λp = 1 for some i = p and is zero for
i 6= p. For a mixed state, however, let us write ρ = pi ρi with ρi being a pure state density
matrix, we have ρ2 = i,j pi pj ρi ρj . The trace of ρ is still 1 as (trace can be calculated in
P

any basis)
XX
tr(ρ) = pi hej |ψi ihψi |ej i
j i
X
= pi hψi |ej ihej |ψi i
i,j
X X
= pi hψi |ψi i = pi = 1
i i
c D. K. Ghosh, IIT Bombay 9

where, in the last but one step we have used the completeness relation. However, for a
mixed state the trace of ρ2 is always less than one, as can be seen in the following:
XX
tr(ρ2 ) = pi pj hek |ρi ρj | ek i
k i,j
X
= pi pj hek |ψi ihψi |ψj ihψj |ek i
i,j,k
X
= p2i hψi |ek ihek |ψi i
i,k
X
= p2i ≤ 1
i

where the equality is applicable only when one of the pi s is equal to one and the others
zero, i.e. a pure state. Thus for mixed states tr(ρ2 ) ≤ tr(ρ).

4 Postulates of Quantum Mechanics - in Density Ma-

trix Language
We have seen that the advantage of the density matrix formulation over the state vector
description lies in the former’s ability to provide a description of open systems. This
is because our system of interest is usually a sub-system which interacts with the envi-
ronment. In such situations, it is not possible to associate a ray with the system under
investigation. The density matrix, on the other hand, can take care of both open systems
or closed systems. It is therefore, necessary to reformulate the quantum postulates in
terms of the density matrix.

1. A quantum system is completely described by a density operator (matrix) ρ which

is a positive operator with unit trace, which acts on the state space of the
system.

2. A closed system evolves unitarily,

ρ(t) = U (t, t0 )ρ(t0 )U † (t, t0 )

3. Outcome of a measurement is probabilistic, the only possible outcomes are eigen-

values λm of the operator representing the observable and the probability of this
measurement is given by
P (m) = hφm |ρ| φm i
where | φm i is the eigenstate corresponding to the eigenvalue λm . Note that in case
of a pure system, this boils down to the Born postulate, since

P (m) = tr (hφm |ψihψ |φi) =| hφm |ψi |2

c D. K. Ghosh, IIT Bombay 10

P
For a mixed state with ρ = i pi | ψihψi |, we obviously can generalise this to
X X
P (m) = pi | hφm |ψi |2 = pi hφm |ψi ihψi |φm i = hφm |ρ| φm i
i i

However, the last expression is equal to tr(ρ | φm ihφm |≡ tr(ρPm ), where Pm =|

φm iφm is the projection operator for the eigenstate | φm i. Later, we will rewrite
this postulate in terms of the measurement operators.

4. The post measurement state of the system is given by

1
ρ(λm ) = | φm ihφm | hφm |ρ| φm ihφm | (8)
p(λm )
Note that as per the state postulate, the post measurement state is given by
P | ψi Pm | ψi Pm | ψi
p m = 1/2
= √
2
hψ |Pm | ψi [hψ |Pm | ψi] pm

Clearly, the density matrix corresponding to the above is given by (??).

5 Reduced Density Matrix

As we have mentioned earlier, frequently, our system of interest A is a part of a larger
system with which it interacts. The quantum coo relations that exist within our system
of interest would decohere as a result of interaction with the environment. If the entire
system (A+ the environment, which we label as B). is described by a density matrix,
the properties of A is obtained by taking partial trace (i.e. averaging) over the trace of
the environment. We will illustrate the basic concept of the reduced density matrix by
considering A to be a one bit system and B also to be a one bit system. Since we would
like to make our measurements only on the system A, it is of interest to see, how things
change if we were to make a measurement on the composite system (A+B) described by
a single density matrix ρAB . We define the reduced density matrix for the system A
by
ρA = trB (ρAB )
where trB is the partial trace over B, defined by

tr (| a1 iha2 | ⊗ | b1 ihb2 |) =| a1 iha2 | tr(| b1 ihb2 |)

where {b1 , b2 } are the (pure) states of B. Now,

X
tr | b1 ihb2 |= hi |b1 ihb2 |ii = hb2 |b1 i
i

We will see that the reduced density matrix provides proper measurement statistic for
the system A. Why do we need partial trace in dealing with composite system?
c D. K. Ghosh, IIT Bombay 11

Let M be an observable on system A while M̃ be the same measurement done on system

AB. We need to show that M̃ = M ⊗ IB . Let our composite system is prepared in the
state | mi⊗ | ψi, where | mi is an eigenstate of A and | ψi is an arbitrary state of B.
Suppose we perform a measurement on the composite system. If Pm is the projector for
| mi on the eigenspace of M , the projector for M̃ s Pm ⊗ IB . Hence
X
M̃ = mPm ⊗ IB = M × IB
m

We should get the same result whether we calculate the result of measurement through
ρA or ρAB , we must have

tr(ρA M ) = tr(ρAB M̃ ) = tr ((M ⊗ IB )ρAB )

One can see that if we take ρA = trB (ρAB ), above equation is satisfied.
Example 1:
Let ρAB = ρ ⊗ σ where ρ is the density operator for A and σ for B. We can see that

ρA = trB (ρ ⊗ σ) = ρ tr(σ) = ρ

(as tr(σ) = 1. Likewise, we can show that ρB = trA (ρAB )).

Example 2:
| 00i+ | 11i
Consider the density matrix corresponding to the Bell state √ which is a two
2
qubit entangled state.
1
ρ= (| 00ih00 | + | 11ih00 | + | 00i | 11i+ | 11ih11 |)
2
Let us trace over the second qubit

ρ1 = tr2 ρ
= 2 h0 |ρ| 0i2 + 2 h1 |ρ| 1i2
1
= [(| 0ih0 | [h0 |0ih0 |0i + h1 |0ih0 |1i]+ | 1ih0 | [h0 |1ih0 |0i + h1 |1ih0 |1i]
2
+ | 0ih1 | [h0 |0ih1 |0i + h1 |0ih1 |1i]+ | 1ih1 | [h0 |1ih1 |0i + h1 |1ih1 |1i]])
1 I
= [| 0ih0 | + | 1ih1 |] =
2 2
Note that tr ρ1 = 1 but tr(ρ21 ) = tr(I 2 /4) = 1/2, i.e. it is a mixed state!. It may be
noted that the original two qubit state is a pure state but the reduced density matrix
corresponds to a mixed state. This is a consequence of quantum entanglement.
c D. K. Ghosh, IIT Bombay 12

6 Schmidt Decomposition and Schmidt Number

An arbitrary vector in the composite space HA ⊗ HB can obviously be expressed in terms
of an orthonormal basis {| φA B
i i} for HA and an orthonormal basis {| φµ i} for HB ,
X
| ψi = Ci,µ | φB B
i i⊗ | φµ i
i,µ
√
The coefficients Ci,µ are, in general, complex and has the form pi,µ eiϕiµ . If HA has the
dimension m and HB has dimension n, the composite system has dimension mn.
The Schmidt decomposition tells us that we can always find a pair of basis {| φ̃A i i} and
B
{| φ̃i i} such that all the cross terms in the expansion of | ψi vanish and we have
X√
| ψi = pi | φ̃A B
i i⊗ | φ̃i i
i
√
such that all coefficients pi are real and the dimension of the space is min(m, n).
Example:
1
Express | ψi = (| 00i+ | 01i+ | 10i+ | 11i) in Schmidt basis.
2
Note that the computational basis for HA and HB are not Schmidt basis because of
presence of cross terms like | 01i and | 10i. However, if we choose
1 1
| φ̃A
0i = √ (| 0i+ | 1i); | φ̃A1i = √ (| 0i− | 1i)
2 2
B 1 B 1
| φ̃0 i = √ (| 0i+ | 1i); | φ̃1 i = √ (| 0i− | 1i)
2 2
A B
We can write | ψi =| φ̃0 i⊗ | φ̃0 i, which does not have any cross term.

Define | φ̃B B A B
P P
i i = µ Ci,µ | φµ i so that | ψi = i | φi i⊗ | φ̃i i. Note that the set
{| φ̃B
i i} may be neither normalised nor orthogonal. However, we could, without loss of
generalty choose the basis {| φA
i i} such that ρA is orthogonal in this basis. Thus
X
ρA = pi | φA A
i ihφi | (9)
i

However, we can calculate ρA as a reduced density matrix from the expression for the
density matrix of the composite system.
ρA = trB ρAB
= trB (| ψiAB AB hψ |)
" #
X  
= trB | φA B
i i⊗ | φ̃i i hφA B
j | ⊗hφ̃j |
i,j
X
= (| φA A B B
i ihφj |) tr((| φ̃i ihφ̃j |)
i,j
X
= (| φA A B B
i ihφj |)hφ̃j |φ̃i i (10)
i,j
c D. K. Ghosh, IIT Bombay 13

where we have used tr((| φ̃B B B B

i ihφ̃j |) = hφ̃j |φ̃i i . However, we have also obtained (??) for
ρA . Thus, on comparing (??) and (??), we get
X X
pi | φA
i ihφA
i |= (| φA A B B
i ihφj |)hφ̃j |φ̃i i
i i,j

This shows that hφ̃B B

j |φ̃i i = pi δi,j , i.e., the new basis is orthogonal. Assuming π 6= 0, we
can normalise it so that
1
| φ̃B
i i → √ | φ̃B
i i
pi
Thus X√
| ψiAB = pi | φiA ⊗ | φ̃B
i i
i

We can take partial trace over A to get ρB

ρB = trA (| ψAB ihψAB |)

!
X√
= trA pi pj | φA A B B
i ihφj | ⊗ | φ̃i ihφ̃j |
i,j
X
= pi | φ̃B B
i ihφ̃i |
i

which shows that ρA and ρB have the same non-zero eigenvalues. This does not imply
that HA and HB have the same dimension as the number of zero eigenvalues may differ.
The number of non-zero eigenvalues of ρA and ρB is known as the Schmidt Number. If
a state is separable, the Schmidt number is 1.

Example 1:
| 01i− | 10i
Let | ψi = √ . Is this state separable?
2
1
ρ =| ψihψ |= [| 01ih01 | − | 01ih10 | − | 10ih01 | + | 10ih10 |]
2
1 1
Taking partial trace, we get ρA = trB ρ = I which has two eigenvalues λ1 = λ2 = .
2 2
Since there are two non-zero eigenvalues, the state is not separable and is entangled.
Example 2:
Check the separability of the state
1 1 i i
| ψi = | 00i + | 01i + | 20i + | 21i
2 2 2 2
where | 0i, | 1i and | 2i constitute an orthonormal set in HA and | 0i and | 1i form a set
on HB .
c D. K. Ghosh, IIT Bombay 14

It is easy to check that taking partial trace over B, gives us ρA to be

1 1 i i
ρA = trB ρ = | 0ih0 | + | 2ih2 | − | 0ih2 | + | 2ih0 |
2
 2 2 2
1 i
− 
=  2i 2

1 
2 2
which has eigenvalues 1 or 0. The non-zero eigenvalue is only 1. Hence the state is
separable. One can directly check that
| 0i + i | 2i | 0i+ | 1i
| ψi = ( √ )⊗( √ )
2 2

7 Purification
We have seen that taking partial trace of a pure state gives us a mixed state. Is the
converse true? Is it possible to to find a pure state density matrix, whose partial trace
yields a given mixed state density matrix? The answer is yes. The process is called
purification.
P
Let ρa = k pk | ψk ihψk | be a density matrix of A in the Hilbert space HA . Introduce a
second Hilbert space HB which has the same dimension as that of HA . Define
X√
| ψi = pk | ψk i⊗ | φk i
k

where {| φk i} is an orthonormal basis in HB . Now,

X√
trB | ψihψ | = trB pk pl | ψk iA A hψl |⊗ | φk iB B hφl |
k,l
X√
= pk pl | ψk iA A hψl |hφk |φm i
k,l
X√
= pk pl | ψk iA A hψl |δk,l
k,l
X
= pk | ψk iA A =ρA
k

Example:
1
Let ρA = (| 0ih0 | +3 | 1ih1 |). Find a purification.
4
Now,  
1 1 0
ρA =
4 0 3
Let | 0i and | 1i be a basis for B. Define
√
1 3
| ψi = | 0iA × | 0iB + | 1iA ⊗ | 1iB
2 2
c D. K. Ghosh, IIT Bombay 15

The tensor product matrix can be seen to be

   √   
1 1 1 3 0 0
| ψi = +
2 0 0 2 1 1
  √  
1 1 0 3 0 0
= +
2 0 0 2 0 1
 
1 1 0
= √
2 0 3

Thus
  
11 0 1 0
| ψihψ | = √ √
40 3 0 3
 
1 0 0 0
√
1 0

3 0 0

=  √
4 0 0 3 0

0 0 0 3
 Wigner representation
Masatsugu Sei Suzuki
Department of Physics, SUNY at Binghamton
(Date: January 13, 2017)

Wigner distribution function in the phase space is a special representation of the density
matrix. It provides a third, alternative, formulation of quantum mechanics, independent of the
conventional Hilbert space or path integral formulations. It is useful in describing transport in
quantum optics, quantum computing, de coherence, and chaos.
Here we discuss the fundamental properties of the Wigner distribution function.

1. Definition of Wigner function

The Wigner distribution function is a quasi-probability distribution function in phase space
( x, p ) and is defined by

1
W ( x, p ) 
  dy * ( x  y )e 2ipy /  ( x  y )

1
 
W ( x, p )  dq * ( p  q)e  2ixq /  ( p  q)

It is a generating function for all spatial autocorrelation function of a given quantum mechanica;
wave function  (x ) . We have different expressions for W ( x , p ) , but these expressions are
equivalent to the above expression.

1
 
W ( x, p )  dy * ( x  y )e  2ipy /  ( x  y )

and

1 y y
W ( x, p ) 
2  dy * ( x  )e  ipy /  ( x  )
2 2
Note

1
W ( x, p ) 
  dy  x  y e 2ipy /  x  y 

1

  dy  dp1dp2  p1 p1 x  y e 2ipy /  x  y p2 p2 
i i
1 1  p1 ( x  y ) p ( x y )
    p2 
 2 ipy /   2
dy dp dp p e e e
 2 1 2 1

1 i i
2 2 
 dy  dp1dp2  p1 p2  exp[ (  p1  p2 ) x  (2 p  p1  p2 ) y ]
2   

We note that

i 2 p  p1  p2
 dy exp[  (2 p  p 1  p2 ) y ]  2 (

)  2 (2 p  p1  p2 )

1 2i
W ( x, p ) 
  dp1  p1 2 p  p1  exp[ ( p  p1 ) x]


When we use p1  p  q , we have

2 p  p1  2 p  ( p  q )  p  q , p  p1   q

Thus we get

2i
1  qx

 
W ( x, p )  dq  p  q e 
pq
2i
1  qx
     ( p  q)
*
dq ( p q ) e 


where the Fourier transforms are defined as

 i
1  px
p    dx p x x    dxe  x 
2

i
1 px
x    dp x p p    dpe  p 
2

Formula:

 dpe  2 ( y )
 iyp

Using the density operator (which include mixed states), the Wigner distribution function can be
rewritten as

2 ipy
1
 
W ( x, p )  e  dy * ( x  y ) ( x  y )
2 ipy
1
 
 e  dy  x  y x  y 
2 ipy
1

  e 
dy x  y   x  y
2 ipy
1
 
 e 
dy x  y ˆ x  y

or

2 ipy
1
 
W ( x, p )  e 
dy x  y ˆ x  y

or

ipy
1 y y
W ( x, p ) 
2  e  dy x  ˆ x 
2 2
When the variable y is replaced by y '   y , the above integral can be rewritten as

 2 ipy '
1 
W ( x, p )  
 
e 
( dy ' ) x  y ' ˆ x  y '

 2 ipy '
1 

 
 e 
dy ' x  y ' ˆ x  y '

or

 2 ipy
1 
W ( x, p )  
  
e 
dy x  y ˆ x  y

or

 ipy
1  y y
W ( x, p )  
2  
e 
dy x  ˆ x 
2 2

or

 ipy
1 y y
W ( x, p )  
2  
e  dy x  ˆ x 
2 2

Note that the density operator is defined by

ˆ    for the mixed state.

and

ˆ    for the pure state.

2. Momentum space expression
Similarly, we have

2i
1  qx
W ( x, p ) 
  dq  p  q e  p  q 
2i
1   qx
 
 e dq p  q ˆ p  q

or

2i
1 qx

 
W ( x, p )  e 
dq p  q ˆ p  q

3. Expression of the density operator

The density operator can be expressed by

2 ips
̂   ds  dxdp x  s P( x, p)e 
xs

((Proof))

2ip ' s '

x  y ˆ x  y   ds' dx' dp x  y x' s ' W ( x' , p' )e 
x' s ' x  y
2 ip ' s '
  dp'W ( x' , p' )e 
dx' ds' x  y x' s ' x' s ' x  y
2 ip ' s '
  dp' dx' ds'W ( x' , p' )e 
 ( x' x) ( s' y )
2 ip ' y
  dp'W ( x, p' )e 

2 ipy
  dpW ( x, p)e 

or
 ipy
y y
x ˆ x    dpW ( x, p )e 
2 2

or

ipy
y y 
x ˆ x    dpW ( x, p)e 
2 2

or

ip ( x  x ' )
x  x' 
x ˆ x'   dpW ( , p )e 
2

In fact, we have the same expression such that

2 ipy 2 ipy
1
 dpW ( x, p)e 
  dpe 
 
dy ' e 2ipy ' x  y ' ˆ x  y '
2 ip ( y  y ')
1
 
 dy ' x  y ' ˆ x  y '  dpe 

1
 
 dy ' x  y ' ˆ x  y '  ( y  y ' )

 x  y ˆ x  y

4. Mathematica properties
(i) The function P ( x , p ) is a real valued function.
((Proof))
  2 ipy
1
 
W ( x, p )*  e 
dy x  y ˆ  x  y

 2 ipy
1
 
 e 
dy x  y ˆ x  y

 2 ipy
1 
 
  
e 
dy x  y ˆ x  y

 W ( x, p )

since ˆ   ˆ .
______________________________________________________________________________

(ii)  dpW ( x, p) 

x ̂ x

If the system can be described by a pure state


2
 dpW ( x, p)  x 


((Proof))
   2 ipy
1 


dpW ( x , p )    

dp e 
dy x  y ˆ x  y

  2 ipy
1 
  dy x  y ˆ x  y  dpe 


  

  dy x  y ˆ x  y  ( y )


 x ˆ x

where

 2 ipy
1  1  2y  1 
 dpe 
 2    2   y     y 
        2
______________________________________________________________________________

(iii)  dxW ( x, p) 

p ̂ p

If the system can be described by a pure state


2
 dxW ( x, p) 

p .

((Proof))

  2i
qx
 dxW ( x, p)   dx  e  dq p  q ˆ p  q
 
 2i
1 qx
  dq p  q ˆ p  q
 

dxe

  dq p  q ˆ p  q  (q)
 p ˆ p

where

 2i
1 qx 1 2x 1 

  
dxe  

2 ( ) 
 
2  ( x )   ( x )
2

______________________________________________________________________________
 
(iv) 

dx  dpW ( x, p )  Tr[ ˆ ]  1


((Proof))

  

 dp  dxW ( x, p)   dp
  
p ˆ p  Tr[ ˆ ]  1
(v) Time reversal operator

ˆ   x
x
*
  x ,

Under the time reversal, W ( x, p )  P ( x, p )

((Proof))

1
W ( x, p ) 
  dy * ( x  y )e 2ipy /  ( x  y )

1

  dy ( x  y )e 2ipy /  * ( x  y )

1

  dy ( x  y )e  2ipy /  * ( x  y )

1

  dy * ( x  y )e  2ipy /  ( x  y )

 W ( x, p )

(vi) Parity operator

x ˆ    x 

Under the parity reversal [ ( x )   (  x ) )

W ( x, p )  W (  x, p )

((Proof))
 1
 
W ( x, p )  dy * ( x  y )e 2ipy /  ( x  y )

1
  dy * ( x  y )e 2ipy /  ( x  y )

1

  dy * ( x  y )e  2ipy /  ( x  y )

 W (  x,  p )

(vii) Translation operator

x Tˆ a   x  a    ( x  a)

Under the translation operator

W ( x, p )  W ( x  a, p )

((Proof))

1
W ( x, p ) 
  dy * ( x  y )e 2ipy /  ( x  y )

1

  dy * ( x  y  a )e 2ipy /  ( x  y  a)

 W ( x  a, p )

___________________________________________________________________________

((Proof))

  i i i
ˆ      Hˆ    Hˆ    [ Hˆ , ˆ ]
t t   
 
 1 ˆ
t
P ( x, p )  
  
e  2ipy /  dy x  y
t
x y


2i
 1 2i  qx
  
W ( x, p )  qe dq p  q ˆ p  q
x

5. State overlap
The state overlap can be calculated as

2  dx  dpW ( x, p)W ( x, p )  Tr[ ˆ ˆ ]

In the case of pure states,

2
2  dx  dpW ( x, p )W ( x, p)  Tr[ ˆ ˆ ]   

((Proof))

1 1
I  2  dx  dp[  dy1e 2ipy1 /  x  y1 ˆ x  y1 ][  dy2e 2ipy 2 /  x  y2 ˆ x  y2 ]
 

( y1  y2 ) 
 dpe   dpe 2ip ( y1  y 2 ) /   2 (2 )  2  ( y1  y2 )
2 ipy1 /  2 ipy 2 / 
e
 2

I  2 dx  dy1 x  y1 ˆ x  y1  dy2 x  y2 ˆ x  y2  ( y1  y2 )

 2 dx  dy1 x  y1 ˆ x  y1 x  y1 ˆ x  y1

We use new variables such that

x  y1  x1 , x  y1  x2
or

1 1
x ( x1  x2 ) , y1  ( x2  x1 )
2 2

 ( x, y1 )
dxdy1  dx1dx2
 ( x1 , x2 )

Jacobian:

x x 1 1
 ( x, y1 ) x1 x2 2 1
  2
 ( x1 , x2 ) y1 y1

1 1 2
x1 x2 2 2

Then we get

I   dx1  dx2 x1 ˆ x2 x2 ˆ x1

  dx1 x1 ˆ ˆ x1
 Tr[ ˆ ˆ ]
 Tr[     ]
2
  

6. Phase space average  Ĝ 

Operator expectation values (averages) are calculated as phase space averages of the
respective Wigner transforms

 py
y ˆ y i
g ( x, p )  

dy x 
2
G x e 
2
(definition)
 Gˆ   Gˆ   Tr[ ˆGˆ ]   dx  dpW ( x, p) g ( x, p) (phase space average)

((Proof))

I   dx  dpW ( x, p ) g ( x, p)
2 ipy1  py 2
1 / y2 ˆ y i
  dx  dp[
  1
dy e 
x  y1 ˆ x  y1 ][  dy2 x  G x 2 e 
]

2 2

y2
2 ip ( y1  )
2 ipy1
2 y1  y2 )
py 2
/ i 2
 dpe 
e 
  dpe 
2 (

)   (2 y1  y2 )


1 y y
I  dx  dy1[  dy2 x  y1 ˆ x  y1 x  2 Gˆ x  2  (2 y1  y2 )
 
2 2
  dx  dy1 x  y1 ˆ x  y1 x  y1 Gˆ x  y1

We use new variables such that

x  y1  x1 , x  y1  x2

or

1 1
x ( x1  x2 ) , y1  ( x2  x1 )
2 2

 ( x, y1 )
dxdy1  dx1dx2
 ( x1 , x2 )

Jacobian:
 x x 1 1
 ( x, y1 ) x1 x2 2 1
  2
 ( x1 , x2 ) y1 y1

1 1 2
x1 x2 2 2

Then we have

I   dx1  dx2 x1 ˆ x2 x2 Gˆ x1   dx1 x1 ˆ Gˆ x1  Tr[ ˆ Gˆ ]

Note that

Tr[ ˆ Gˆ ]  Tr[   Gˆ ]  Tr[  Gˆ  ]   Gˆ 

i
7. Expression of g ( x, p) for the operator Gˆ  exp[ (xˆ  pˆ )]

i
We calculate g ( x, p ) for the operator Gˆ  exp[ (xˆ  pˆ )] .



ipy y i y
g ( x, p )   dy exp( 

) x
2
exp[ (xˆ  pˆ )] x 
 2

ipy y i ixˆ ipˆ y
  dy exp( 

) x
2
exp(
2
) exp( ) exp( ) x 
  2

i ipy i y y ipˆ y
 exp( )  exp( ) exp[ ( x  )]dy x  exp( ) x 
2     2 2  2

i ipy i y y y
 exp( )  exp( ) exp[ ( x  )]dy x  x   
2     2 2 2

i ipy i y
 exp( )  exp( ) exp[ ( x  )]dy ( y   )
2     2
i  
 exp[ (  p   ( x  )]
 2 2

or
 i
g ( x, p)  exp[ (x  p )]


((Note))
(i) The Baker-Campbell-Haussdorff theorem

i
Gˆ  exp[ (xˆ  pˆ )

ixˆ ipˆ 
 exp( ) exp( ) exp[ 2 [ xˆ, pˆ ]
  2
i ixˆ ipˆ
 exp( ) exp( ) exp( )
2  

ipˆ
(ii) Translation operator exp( )


ipˆ y y
exp( ) x  x  
 2 2

7. Fourier transform of the Wigner function

 Gˆ   Gˆ 
i
 exp[ (xˆ  pˆ )

i ixˆ ipˆ
  dxdx'  x x exp( ) exp( ) exp( ) x' x' 
2  
i ix ipˆ
 exp( )  dxdx' exp( )  x x exp( ) x' x' 
2  
i ix
 exp( )  dxdx' exp( )  x x x' x' 
2 
i ix
 exp( )  dx exp( )  x x   
2 
i 
  dx exp[( ( x  ) * ( x) ( x   )
 2
ix
 
  dxe  * ( x  ) ( x  )

2 2

or

i
Gˆ  exp[ (xˆ  pˆ )

ix
 
  dxe   * ( x  ) ( x  )
2 2
i (x  p )
  dxdp exp[ ] P ( x, p )

 C ( , )

where

ipˆ ipˆ
exp( ) is the translation operator; exp( ) x'  x'
 

x x'   ( x' x   )

7. Fourier transform of W ( x , p )
 ix
i (x  p)  
 dxdp exp[ 
]W ( x, p)   dxe   * ( x  ) ( x  )
2 2

((Proof))

i (x  p)
 dxdp exp[ 
]W ( x, p)

i (x  p) 1 y y
  dxdp exp[ ]  dy * ( x  )e  ipy /  ( x  )
 2 2 2
ix ip ( y  )
1 y y 

2  dxdy * ( x  )e   ( x  )  dpe 
2 2
ix
1 y y

2  dxdy * ( x  )e   ( x  )2 ( y   )
2 2
ix
 
  dxe   * ( x  ) ( x  )
2 2

where

1 y y
W ( x, p ) 
2  dy * ( x  )e  ipy /  ( x  )
2 2

Thus we have

i
Gˆ  exp[ (xˆ  pˆ )

ix
 
  dxe  * ( x  ) ( x  )

2 2
i (x  p )
  dxdp exp[ ]W ( x, p )


8. The matrix element x Gˆ y

 The Wigner transformation is a general invertible transformation of an operator Ĝ on a
Hilbert space to a function g ( x , p ) on phase space, and is given by

 ps
s ˆ s i
g ( x, p ) 

 ds x 
2
G x e 
2
(definition)

 ip ( x  y )
1 x y
2 
I dpe 
g( , p)
2
  ip ( x  y )
x y s ˆ x y s
ps
1 i
 
2  
ds
2
 G
2 2

2  dpe


e 


1 x y s ˆ x y s
 
2  
ds
2
 G
2 2
 2 ( x  y  s )
2

x y s ˆ x y s
  ds

2
 G
2 2
  ( x  y  s)
2
 x Gˆ y

or

 ip ( x  y )
1 x y
x Gˆ y 
2 
dpe 
g( , p) .
2

Hermitian operators map to real functions. The inverse of this transformation, so from phase
space to Hilbert space, is called the Weyl transformation.

9. Size of quantum state

When we consider two identical density operators, ˆ  ˆ  ˆ and recall that

Tr[ ˆ 2 ]  1

where the equal sign holds only for a pure state. So we get from
 2  dx  dp[W ( x, p)]2  Tr[ ˆ 2 ]  1

or

1
2 
 dx dp[W ( x, p)]
2

Note that the area A of x-p phase space where the function P ( x, p ) takes on considerable values
follows as

1
A .
 dx dp[W ( x, p)]
2

10. Upper bound of Wigner function

For the pure state,

1 y y
W ( x, p ) 
2  dy * ( x  )e  ipy /  ( x  )
2 2

1
 dy1 ( y )2 ( y )
*

  
1
  
 1 2

where

1 ipy y 1 y
1 ( y )  e  (x  ) , 2 ( y )   (x  )
2 2 2 2

  2 
1 y
1 1   1 ( y) dy   2  ( x  2 ) dy   ( ) d  1
2 2


   2 
1 y
2 2   2 ( y ) dy   2  ( x  2 ) dy   ( ) d  1
2 2



These definitions allow one to estimate the Wigner function

1
W ( x, p )   
 1 2

With the help of the Cauchy-Schwartz inequality

2
1 2  1 1 2 2  1

valid for two normalized states 1 and 2 . The Wigner function of a pure normalized state

1
cannot take on values larger than .


11. Wigner function can take on negative value

For the case of two density operators ̂ 1 and ̂ 2 such that

Tr [ ˆ1ˆ 2 ]  0

This relation implies

2  dx  dpW ( x, p )W ( x, p)  Tr[ ˆ ˆ ]  0

That is the product of the two Wigner functions integrated over the whole phase space has to
vanish. This condition enforces that the Wigner function W ( x, p) or / and W ( x, p) must take

on negative values. This surprising feature makes it impossible to interpret the Wigner function
as a true probability as a true probability distribution. Nevertheless, the Wigner function is useful
to calculate the quantum mechanical expectation values.
12. Derivation of the wave function from the Wigner function
(i) Fourier transform of W ( x1 , p )

 2 ip
 s
W ( x1 , s )   dpP( x1 , p)e 


 2 ip 2 ipy
 s 1
  dpe


  dy * ( x1  y )e 
 ( x1  y )

1 2

  dy * ( x1  y ) ( x1  y )2 [ ( s  y )]

1

  dy * ( x1  y ) ( x1  y ) ( s  y )

  * ( x1  s ) ( x1  s )

where

1
W ( x, p ) 
  dy * ( x  y )e 2ipy /  ( x  y )

x  x0  x  x0
When x1  , s ,
2 2

x  x0  x  x0
W( , )   * ( x0 ) ( x)
2 2

or

x  x0  x  x0
W( , )
 ( x)  2 2 (1)
 * ( x0 )

(ii) The choice of x1  x0 and s = 0 yields

 W ( x0 ,0)   * ( x0 ) ( x0 )

or

W ( x0 ,0)
 * ( x0 )  (2)
 ( x0 )

Using Eqs.(1) and (2),

x  x0  x  x0
W( , )
 ( x)  2 2  ( x0 ) (3)
P ( x0 ,0)

P is pure real while  is generally complex.

13. von Neumann equation in phase space (from Toda, Kubo, and Saito)
The equation of motion for the density operator;

ˆ   

ˆ   
   
t t t
 
   
t t
i i
  Hˆ      Hˆ
 
i
  [ Hˆ , ˆ ]


Thus we have
  y y y ˆ y i y y
x  ˆ x   x x   x  [ Hˆ , ˆ ] x 
t 2 2 2 t 2  2 2

ipy
1 
We multiply both sides by e and integrate over the variable y.
2

ipy
1  y y
2 
W ( x, p )  dye 
x ˆ x 
2 2

The equation of motion:

W ( x, p) y ˆ
ipy
1  y
t

2  dye 
x
2 t
x
2
ipy
1  y i ˆ y

2  dye 
x  [ H , ˆ ] x 
2  2
ipy
i  y y
 2 
dye  x  ( Hˆ ˆ  ˆHˆ ) x 
2 2 2

We assume that the Hamiltonian Ĥ is given by

1 2
Hˆ  pˆ  V ( xˆ )
2m

1 2 1 2
x' [ Hˆ , ˆ ] x"  x' [ pˆ  V ( xˆ )]ˆ  ˆ [ pˆ  V ( xˆ ))] x"
2m 2m
2 2 2
 [ ( 2 )  V ( x' )  V ( x" )]} x' ˆ x"
2m x' x"2

If we change the variables as

y y
x'  x  , x"  x 
2 2
or

x' x"
x , y  x ' x"
2

Using

 x  y  1  
    ,
x' x' x x' y 2 x y

 x  y  1  
   
x" x" x x" y 2 x y

we get

2 2 2
 ( 2 )  V ( x' )  V ( x" )
2m x' x"2
2 1   1   y y
 [(  )2  (  ) 2 )]  V ( x  )  V ( x  )
2m 2 x y 2 x y 2 2
2 2 y y
  V (x  )  V (x  )
m xy 2 2

Then we have

W
ipy
i  y 1 2 1 2 y
2 
 dye 
x [ pˆ  V ( xˆ )]ˆ  ˆ [ pˆ  V ( xˆ ))] x 
t 2 2 2m 2m 2
2 2
ipy
i  y y y y
2 
 dye [

 V ( x  )  V ( x  )] x  ˆ x 
2 m xy 2 2 2 2

We note that
   ip 
ipy ipy
 y y  y y
 dye 
y x
x  ˆ x 
2 2

 x  dye  x  ˆ x 
2 2

  
ipy ipy
 y y y y y
e 
V ( x  ) x  ˆ x   V (x  )e 
x ˆ x 
2 2 2 2i p 2 2

Thus we have

W
ipy
i  y 1 2 1 2 y
2 
 dye 
x [ pˆ  V ( xˆ )]ˆ  ˆ [ pˆ  V ( xˆ ))] x 
t 2 2 2m 2m 2
2 2
ipy
i  y y y y
2 
 dye 
[   V ( x  )  V ( x  )] x  ˆ x 
2 m xy 2 2 2 2
 2  ip
ipy
i  y y
2 
 dye [

x  ˆ x  ]
2 m x  2 2
    
ipy
i y y
2 
 dy[V ( x  )  V (x  )]e 
x ˆ x 
2 2i p 2i p 2 2
p  1
ipy
 y y

m x 2  dye  x  ˆ x 
2 2
   
ipy
1 1  y y
2i p 2 
 [V ( x  )  V (x  )] dye 
x ˆ x 
i 2i p 2 2

or

W p  1    
 W  [V ( x  )  V (x  )]W (1)
t m x i 2i p 2i p

which is the Liouville equation in the Wigner representation. If we take the classical limit , the
operator   0 , the operator on the right-hand side of Eq.(1) reduces to the Liouville operator,
since

1     V 
[V ( x  )  V (x  ) ,
i 2i p 2i p x p
or

W p W V W
  .
t m x x p

((Note))

The equation of motion for each point in the phase space is classical in the absence of forces

 p 
W ( x, p )   W ( x, p ) .
t m x

14. Wigner distribution function for simple harmonics

The wave function of the simple harmonics with state n

1 2
 
n ( )   n  (  2 n!) e
n 2 2
H n ( )

where

1 1
 n ( )   n  xn   n ( x)
 

m0



H n ( ) is the Hermite polynomial.

In the phase space variables x and p the Wigner function of the n-th energy eigenstates is given
by

(1) n p p
Fn ( x, p )  exp{[( ) 2  (  x) 2 ]}Ln {2[( ) 2  (  x) 2 ]}
  

or

(1) n p p
Fn ( x, p )  exp{[( ) 2  (  x) 2 ]}Ln {2[( ) 2  (  x) 2 ]}
  

Ln (x) is the Laguerre polynomial.

  x (dimensionless)

p
 (dimensionless)


since

     1 
p   
i x i x  i 

15. Operator Ordering in Quantum Mechanics: symmetrical operator

 
ipy y y
xˆpˆ   dy exp( 

) x
2
xˆpˆ x 
2

ipy y y y
  dy exp( 

)( x  ) x  pˆ x 
2 2 2

ipy y y y
  dy exp( 

)( x  )  p' dp ' x  p'
2 2
p' x 
2

ipy y y y
  dy exp( 

)( x  )  p' dp ' x  p'
2 2
p' x 
2

1 ipy y i y i y
 
2  
dy exp( )( x  )  p ' dp' exp[ p ' ( x  )] exp[ p' ( x  )]
 2  2  2

1 ipy y ip ' y
 
2  
dy exp( )( x  )  p ' dp' exp(
 2 
)

 
1 i( p  p' ) y 1 1 i( p  p' ) y
x 
2  
dy  p ' dp ' exp[

] 
2 2  
dy  yp' dp ' exp[

]

1 
 xp  p
2 i p
1
 xp 
2i

where

 
1 i( p  p' ) y 1 i( p  p' ) y

2  
dy  p' dp' exp[

] 
2  
p ' dp' dy exp[

]


1
2 
 p ' dp'2 ( p  p' )

p
 
ipy y y
pˆ xˆ   dy exp( 

) x
2
pˆ xˆ x 
2

ipy y y y
  dy exp( 

)( x  ) x  pˆ x 
2 2 2

ipy y y y
  dy exp( 

)( x  )  p' dp' x  p'
2 2
p' x 
2

ipy y y y
  dy exp( 

)( x  )  p' dp' x  p'
2 2
p' x 
2

1 ipy y i y i y
 
2  
dy exp( )( x  )  p' dp' exp[ p ' ( x  )] exp[ p' ( x  )]
 2  2  2

1 ipy y ip ' y
 
2  
dy exp( )( x  )  p' dp' exp(
 2 
)

 
1 i( p  p' ) y 1 1 i( p  p' ) y
x 
2  
dy  p ' dp ' exp[

] 
2 2  
dy  yp' dp ' exp[

]

1 
 xp  p
2 i p
1
 xp 
2i

Then we have

xˆpˆ  pˆ xˆ 1 1 1
 ( xp   xp  )  xp
2 2 2i 2i

Hence, for this example the Weyl-Wigner ordering corresponds to the symmetric ordering.

xˆpˆ  pˆ xˆ
S ( xˆpˆ ) 
2

where S ( xˆpˆ ) is summed over all possible ordering of x̂ and p̂ .

S ( xˆpˆ )  xp
In general,

S ( xˆ m , pˆ n )   dx  dp( x m p n ) F ( x, p)

For example, if m = 2, n = 2, then

1 2 2
S ( xˆ 2 , pˆ 2 )  ( xˆ pˆ  pˆ 2 xˆ 2  xˆpˆ xˆpˆ  pˆ xˆpˆ xˆ  pˆ xˆ 2 pˆ  xˆpˆ 2 xˆ )
6

REFERENCES
T.L. Curtright, D.B. Fairlie, and C.K. Zachos, A Concise Treatise on Quantum Mechanics in
Phase Space (World Scientific, 2014).
W.P. Schleich, Quantum Optics in Phase Space (Weiley-VCH, 2001).
C.K. Zachos, D.B. Fairlie, and T.L. Curtright (Editors), Quantum Mechanics in Phase Space
(World Scientific, 2005).
M. Suda, Quantum Interferometry in Phase Space (Springer, 2006).
R. Kubo, Wigner Representation of Quantum Operators and its Application to Electrons in a
Magnetic Field, J. Phys. Soc. Jpn. 19, 2127 (1964).
M. Toda, R. Kubo, amd N. Saito, Statistical Physics I (Springer, 1983).
______________________________________________________________________________
APPENDIX
* product

i  i 
f ( x, p ) * g ( x, p )  f ( x  ,p ) g ( x, p )
2 p 2 x

The equivalent Fourier representation of the *-product is

 1
 2 
f *g  dp' dp" dx' dx" f ( x' , p' ) g ( x", p" )

 2i
 exp( [ p( x' x" )  p' ( x" x)  p" ( x  x' )])


An alternative integral representation of this product is

1
 2 
f *g  dx' dx" dp' dp" f ( x  x' , p  p' ) g ( x  x", p  p" )

2i
 exp[ ( x' p" x" p' )]


Note that

 dxdp f * g   dxdpg * f   dxdp fg

((Proof))

1
 dxdpf * g   dxdp    dx' dx" dp' dp" f ( x' , p' ) g ( x" , p" )
2

 2i
 exp( [ p ( x' x" )  p' ( x" x)  p" ( x  x' )])


Note that

p ( x ' x" )  p ' ( x" x )  p" ( x  x ' )  x ( p" p ' )  p ( x ' x" )  ( p ' x" p" x ' )

 2i
 dp exp[ 
p( x' x" )]   ( x' x" ) ,

 2i
 dx exp[ 
x( p" p ' )]   ( p" p ' )
Then we get

1
 dxdpf * g   dxdp    dx' dx" dp' dp" f ( x' , p' ) g ( x", p")
2

 2i
 exp( [ x( p" p ' )  p ( x' x" )  ( p ' x" p" x' )])

 2i
  dp ' dp" dx' dx" f ( x' , p ' ) g ( x", p" ) exp[ ( p ' x" p" x' )]

  ( p" p ' ) ( x' x" )
  dx' dp ' f ( x' , p ' ) g ( x' , p ' )

or

 dxdpf * g   dxdpf ( x, p) g ( x, p)
 Quantum Mechanics - II
Angular Momentum - I : Properties of
Angular Momentum - A brief review
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 2, 2019

1 Introduction
In Quantum Mechanics-I, we had studied the theory of angular momentum. We will start
this lecture with a short review of the basics of angular momentum. We had pointed out
that symmetry of the Hamiltonian under translation leads to conservation of linear mo-
mentum. Likewise, the symmetry of the Hamiltonian under rotation of coordinate system
leads to conservation of the angular momentum. There is, however, a difference between
these two. While elements translations commute (translation group is said be abelian),
finite rotations, in general, do not commute. If, however, one considers infinitesimal rota-
tions, they commute.
  The operator for infinitesimal rotation by an angle dΩ is given by
i~ ~ ~ has a direction along the axis of rotation and L~ is the angular
1 − dΩ · L , where dΩ
~
momentum vector. In classical mechanics, the components of orbital angular momentum
(spin being a purely quantum mechanical entity is not there in a classical description)

1
satisfy the following Poisson bracket relations

{Lz , x} = y
{Lz , y} = −x
{Lz , z} = 0
{Lz , px } = py
{Lz , py } = −px
{Lz , pz } = 0 (1)

which may be compactly written using a rank 3 symmetric tensor ijk ( called Levi
Civita symbol), as
{Li , xj } = ijk xk {Li , pj } = ijk pk (2)
where i = 1, 2, 3 and {xi = x, y, z}. The symbol ijk takes the value 1 if i, j, j is an even
permutation of the indices, −1 for an odd permutation and zero if any air of indices are
equal.
The orbital angular momentum operator in quantum mechanics is a generalization of the
corresponding classical definition by replacing the position vectors by the corresponding
position operators and the momentum vectors by the corresponding hermitian operators
∂
for momentum, viz., by replacing pi → −i~ ,
∂xi
 
∂ ∂
Lx = (~r × p~)x = ypz − zpy → −i~ y −z
∂z ∂y
 
∂ ∂
Ly = zpx − xpz → −i~ z −x
∂x ∂z
 
∂ ∂
Lz = xpy − ypx → −i~ x −y (3)
∂y ∂x
The operators above satisfy commutation relation

[Li , Lj ] = ijk Lk (4)

Strictly speaking, a quantity like L2 which simultaneously involves both position and
momentum is an unlikely candidate to be a constant of motion in quantum mechanics.
Unlike the orbital angular momentum, there is no classical analogy for the spin angular
momentum, which is intrinsically of quantum mechanical origin. However, taking a cue

2
from the discussion above, we define the angular momentum operator Jˆ as generator of
infinitesimal rotation. In analogy with the orbital angular momentum, we define rotation
operator UR (n̂, dθ) which generates rotation by an angle θ about the axis ~n
i
UR (n̂, dθ) = 1 − (Jˆ · n̂)dθ
~

The components of angular momentum Jˆ satisfy the following commutation relation

[Ji , Jj ] = i~ijk Jk (5)

Groups having the above property of their elements and of their generators are called Lie
Groups and the property (5) is called Lie algebra. In general, Lie group can have any
number of generators of which 3 is a special case.

2 Rotational Symmetry and associated SO(3) and

SU(2) Groups
2.1 Orthogonal Group of matrices
Since the rotations involved in the orbital angular momentum are in the real three di-
mensional space R3 , we start by reviewing the properties of rotations in this space.
Rotational transformations are linear, i.e. under rotation, the components of ~r, viz.
(x1 , x2 , x3 ) ≡ (x, y, z) become linear combination of such components before rotation,
3
X
x0k = Rki (θ)xi (6)
i=i

with k = 1, 2, 3. Equation (6) is also applicable for the components of an arbitrary vector
V~ , i.e.
X 3
0
Vk = Rki (θ)Vi (7)
i=i

Thus rotation may be represented by a 3 × 3 matrix R(θ), whose components appear

as the coefficients in the linear transformation mentioned above. For instance, for rotation

3
by an angle θ about the z − axis, the rotation matrix is given by

cos θ − sin θ
 
0
Rz (θ) =  sin θ cos θ 0 (8)
0 0 1

Rotation of a rigid body about an axis may be described by specifying three parameters,
for instance, by specifying three Euler Angles. A property of rotation is that it preserves
the scalar product of vectors, viz., if as a consequence of rotation, a vector V~1 → V~10 and
V~2 → V~20 , then V~1 · V~2 = V~10 · V~20 . Expressing the vector V~ as a column matrix containing
the components of the vector as its elements,
 
Vx
V = Vy 

Vz

We may write (7) as a matrix equation

V 0 = RV

The scalar product of V1 with V2 is obtained by multiplying the transpose matrix of V1 ,

i.e. V1T with V2 . Thus

V~10 · V~20 = V10T V20

= (RV1 )T (RV2 )
= V1T RT RV2

Since the scalar product is invariant, we must have

RT R = I =⇒ RT = R−1

where I is an identity matrix. The above relation implies that the columns of the rotation
matrix are orthogonal. It is easy to see that the transpose relation also holds.

(V10 )T V20 = V1T V2

= (RT V10 )T (RT V20 )
= (V10 )T RRT V20

4
which gives RRT = I. This implies that the rows of R are also orthogonal.
The set of all rotations form a group known as O(3). Since RT R = RRT = I, it follows
that (detR)2 = 1 =⇒ detR = ±1.
The case detR = +1 is called proper rotation. The set of all such rotation form a group
termed SO(3), which stands for the special orthogonal group in 3 dimension. It is a
sub-group of O(3). The group property may be easily verified because

1. product of any two proper rotation is also a proper rotation : Suppose R1 and R2
are two elements which are real 3 × 3 matrices. Let R3 = R1 R2 . Clearly R3 is real.
We also have

R3T R3 = (R1T R2 )T (R1T R2 ) = (R2T R1 )(R1T R2 ) = R2T (R1 R1T )R2 = R2T R2 = I

2. identity element exists, which corresponds to 3 × 3 identity matrix.

3. corresponding every element, there exists an inverse (Rz (−θ) is the inverse of Rz (θ))
: Since detR = 1, the matrix is non-singular and hence the inverse matrix exists.
Inverse belongs to the group SO(3) because inverse of the transpose of a matrix is
transpose of the inverse. Thus (R−1 )T R−1 = (RT )−1 (R−1 ) = (RRT )−1 = I and

4. the group multiplication is associative because matrix multiplication is associative

It is easily seen that the group is non-abelian (i.e. the multiplication is not commutative).
For the case where detR = −1, the matrix for Rz (θ) is obtained by multiplying the
previously given expression for Rz (θ) by −1. Physically this corresponds to a rotation
followed by an inversion about the origin and is termed improper rotation because unlike
the case of proper rotation, which is given by the case where detR = +1, the rotation
cannot be built up by incremental increase from identity. Further, such improper rotations
do not form a group because product of two such rotations give a proper rotation because
detR1 × det R2 = +1 instead of −1.
One of the important aspect of a group is the concept of a generator. A generator, or a set
of generators, is a set of elements of the group whose repeated application on themselves
generate all the elements of the group. To illustrate the concept, consider the matrix
Rz (θ) given in (8). Intuitively, we know that a rotation by an angle θ may be obtained
θ
by incremental rotations about the same axis by an angle δθ = limN →∞ . In this limit,
N
we may express Rz (δθ) as

5
 1 −δθ 0 0 −i 0
   
iδθ 
Rz (δθ) = δθ 1 0 = I − ~ i 0 0
~
0 0 1 0 0 0
where we have extracted a factor −i to make the matrix explicitly hermitian (the factor
~ has been introduced for dimensional reason). thus if we define a hermitian matrix Jz
by
0 −i 0
 

Jz = ~  i 0 0
0 0 0
we may write
 N
iθ
Rz (δθ) = lim 1 − Jz
N →∞ ~N
i
−Jz θ
which is simply e ~ . The other two generators are written similarly, using
 
0 0 0
Jx = ~ 0 0 −i
0 i 0

and  
0 0 i
Jy = ~  0 0 0
−i 0 0
It may be verified that Jx , Jy , Jz satisfy

[Ji , Jj ] = i~ijk Jk (9)

which is the structure of Lie algebra. The corresponding group is called Lie group. Because
the elementary generators do not commute, it is simple to trivial the expression for the
generator for arbitrary rotation about an axis n̂. However, it turns out that it is given by
i
ˆ
− J·n̂θ
e ~ .

6
2.2 Generators of SU(2) Group
We define the Special Unitary Group SU(2) in a way similar to the way we defined SO(3)
but consisting of 2 × 2 complex, unitary matrices U for which detU = +1. By unitarity
U U † = U † U = I. This group, like SO(3) is also a Lie group. It is easy to show that these
two conditions require the structure of the matrices to have the following structure
 
a b
b∗ −a

where a is real and b, in general, is complex. The real and imaginary parts of b along
with a provide three parameters which specify the group. The matrices are traceless and
hermitian. A representation of these matrices is given in terms of three Pauli matrices
     
0 1 0 −i 1 0
σx = σy = σz =
1 0 i 0 0 −1

These matrices have the following properties :

σx2 = σy2 = σz2 = 1

σi σj = iijk σk
1 ~
The spin S = spin matrices are given in terms of the Pauli matrices by Si = σi .
2 2
Any 2 × 2 matrix may be expressed as a linear combination of these three matrices and
the unit matrix I. The matrices satisfy Lie algebra

[Si , Sj ] = iijk Sk

and are infinitesimal generators of the SU(2) group. In analogy with the generators of
the SO(3) group, we define
i ~ = exp(− i θn̂ · σ̂)
U = exp(− θn̂ · S) (10)
~ 2
In order to show that the above is indeed the generator of SU(2), we need to show that
any complex 2 × 2 may be obtained from it. To do so, let us write Eqn. (10) as a power
series. We have ∞  k
X (−i)k θ
U= (n̂ · σ)k
k=0
k! 2

7
We now split the above into two terms, each an infinite series, one corresponding to even
values of k and the other to odd values. We then use the property σn2 = I, which implies
that (n̂ · σ)2k = I and (n̂ · σ)2k+1 = n̂ · σ. We then have
∞  2k ∞  2k+1
X (−i)2k θ 2k
X (−i)2k+1 θ
U= (n̂ · σ) + (n̂ · σ)2k+1
k=0
(2k)! 2 k=0
(2k + 1)! 2
∞
X (−1) k
  2k ∞
X (−1)k (−i)  θ 2k+1
θ
= I+ (n̂ · σ)
k=0
(2k)! 2 k=0
(2k + 1)! 2
= cos(θ/2)I − sin(θ/2)(n̂ · σ)

Expressed as a matrix, it gives

 
cos(θ/2) − inz sin(θ/2) −(ny + inx ) sin(θ/2)
U=
(ny − inx ) sin(θ/2) cos(θ/2) + inz sin(θ/2)

which, clearly is a unitary matrix with determinant equal to +1.

3 Properties of Angular Momentum Operator

We will obtain eigenvalues of Jz and J 2 operators in this section. It may be verified that
these two operators commute. Define

J± = Jx ± iJy (11)

It is easily verified that

[J+ , J− ] = 2~Jz (12)

[Jz , J± ] = ±~J± (13)

Let the eigenstates of Jz be labeled by m

Jz | mi = m~ | mi (14)

Since Jz and J 2 commute, we may label their common eigenstates by | j, mi, where

J 2 | jmi = j(j + 1)~2 | j, mi (15)

8
where both j and m are yet to be determine. However, since the eigenvalues of J 2 must
be non-negative, we must have j(j + 1) > 0. The states satisfy the orthogonality property

hj 0 , m0 | j, mi = δj,j 0 δm,m0 (16)

Note that
1
J 2 − Jz2 = Jx2 + Jy2 = [J+ J− + J− J+ ]
2
Since each term on the right is of the form A† A, each term is non-negative and hence the
eigenvalues of J 2 − Jz2 are also non-negative. Thus we must have
p p
j(j + 1) − m2 ≥ 0 =⇒ ‘ − j(j + 1) ≤ m ≤ + j(j + 1)

Thus the eigenvalues of Jz are bounded from both below and from above. In order to
determine the two bounds, we proceed as follows.
It can be easily verified that J 2 commutes with each component of angular momentum.
Thus [J 2 , J+ ] = 0. This implies that J+ | j, mi is an eigenstate of J 2 ,

J 2 (J+ | j, mi) = J+ (J 2 | j, mi) = j(j + 1)~2 J+ | j, mi

Thus J+ | j, mi is an eigenstate of J 2 with the eigenvalue j(j + 1)~2 . Note that [Jz , J+ ] =
~J+ . This gives

Jz J+ | j, mi = ~J+ | j, mi + J+ Jz | j, mi
= ~J+ | j, mi + m~J+ | j, mi
= (m + 1)~J+ | j, mi

Thus, J+ | j, mi is an eigenstate of Jz with eigenvalue (m + 1)~. However, the state

| j, m + 1i is also the eigenstate of Jz with the same eigenvalue, viz. (m + 1)~. Thus these
two states must be multiple of one another, i.e.

J+ | j, mi = Cjm | j, m + 1i (17)

where Cjm is a constant, to be determined. Thus the action of the operator J+ , acting on
the state | j, mi is to increase the m value by one unit of ~. This process can be continued
and we may, starting from the state | j, mi, generate a sequence of states J+ | j, mi, J+2 |
j, mi, J+3 | j, mi . . . corresponding, respectively to eigenvalues (m + 1)~, (m + 2)~, (m +

9
3)~, . . .. Since m has an upper limit, this sequence has to terminate at some power p of
J+ , so that J+p | j, mi = 0.
∗
Consider eqn. (17). Hermitian conjugate of the equation gives hj, m | J− = Cjm hj, m |.
Taking a scalar product with (17), we get

hj, m | J− J+ | j, mi =| Cjm |2 (18)

Note that

J− J+ = (Jx − iJy )(Jx + iJy )

= Jx2 + Jy2 + i[Jx , Jy ]
= Jx2 + Jy2 − ~Jz
= J 2 − Jz2 − ~Jz

Using this in (18), we get

| Cjm |2 = hj, m | J 2 − Jz2 − ~Jz | j, mi = j(j + 1)~2 − m2 ~2 − m~2

For the highest value of m,using (17) and J+ | j, mi = 0 for this state, we must have
Cjm = 0. Thus taking the maximum value of m to be mmax , we have

j(j + 1) = m2max + mmax

which gives mmax = j.

In a similar way, by observing that [Jz , J− ] = −J− , we can show that J− | j, mi is
an eigenstate of Jz with eigenvalue (m − 1)~. Following an argument similar to the
above, we can show that starting with the state | j, mi, we may generate a sequence
of states J− | j, mi, J−2 | j, mi, J−3 | j, mi . . . corresponding, respectively to eigenvalues
(m−1)~, (m−2)~, (m−3)~, . . .. Since m has a lower limit, this sequence has to terminate
at some power q of J− , so that J−q | j, mi = 0. We then have

J− | j, mi = Djm | j, m − 1i (19)

where Djm is a constant, to be determined. The Hermitian conjugate of the equation

∗
gives hj, m | J+ = Djm hj, m |. Taking a scalar product with (19), we get

hj, m | J+ J− | j, mi =| Djm |2 (20)

10
Note that

J+ J− = (Jx + iJy )(Jx − iJy )

= Jx2 + Jy2 − i[Jx , Jy ]
= Jx2 + Jy2 + ~Jz
= J 2 − Jz2 + ~Jz

Using this in (20), we get

| Djm |2 = hj, m | J 2 − Jz2 + ~Jz | j, mi = j(j + 1)~2 − m2 ~2 + m~2

For the minimum value of m,using (19) and J− | j, mi = 0 for this state, we must have
Djm = 0. Thus taking the minimum value of m to be mmin , we have

j(j + 1) = m2min − mmin

which gives mmin = −j. (The other solution mmin = j +1 is discarded because mmax = j).
Since the values of m are spaced at unit intervals starting from −j and ending at +j, it
follows j must either be a half integer or an integer. We define, angular momentum to
be given by the value of j, the unit of ~ is understood. We, therefore have the following
properties :
1. Possible values of angular momentum are 0, 1/2, 1, 3/2 2ldots.

2. For a given value of j, the eigenvalues of J 2 are j(j + 1)~2 .

3. For a given j, the eigenvalues of Jz are −j~, (−j + 1)~, . . . , +j~.

3.1 Properties of Raising and Lowering (Ladder) Operators

Define
| ±i = J± | j, mi
In the previous section, we have shown that | ±i are eigenstates of Jz with eigenvalues
(m ± 1)~. However, | j, m ± 1i is also such an eigenstate. Thus we must have these states
are multiples of one another. It was also shown that (Eqns. (17) and (19)) that
p
| +i = J+ | j, mi = j(j + 1) − m2 − m~ | j, m + 1i (21)
p
| −i = J− | j, mi = j(j + 1) − m2 + m~ | j, m + 1i (22)

11
Thus, J± have matrix elements between states which differ in their m values by 1. For
j = 1, the matrix representation of the operators are as follows (the rows and column are
labeled in the order m = +1, 0, −1:)
   
1 0 0 1 0 0
J 2 = 2~2 0 1 0 Jz = ~ 0 0 0  (23)
0 0 1 0 0 −1
Using the properties of ladder operators, we have
J+ | 1, 1i = 0
√
J+ | 1, 0i = 2~ | 1, 1i
√
J+ | 1, −1i = 2~ | 1, 0i
and
√
J− | 1, 1i = 2~ | 1, 0i
√
J− | 1, 0i = 2~ | 1, −1i
J− | 1, −1i = 0
The matrix representation of these operators are
 √   
0 2 0 0 0 0
√ √
J+ = ~ 0 0 2 J− = ~  2 0 0 (24)
√
0 0 0 0 2 0
A special case of interest are the Pauli matrices for spin 1/2, i.e. for j = s = 1/2. The
spin matrices Si are related to the Pauli matrices σi by Si = (~/2)σi , where
     
0 1 0 −i 1 0
σx = σy = σz = (25)
1 0 i 0 0 −1

3.2 Eigenfunctions of Orbital Angular Momentum

In spherical coordinates, the angular momentum operators are expressed as
∂
Lz = −i~ (26)
∂ϕ
1 ∂2
   
2 2 1 ∂ ∂
L = −~ sin θ + (27)
sin θ ∂θ ∂θ sin2 θ ∂ϕ2

12
The normalized eigenfunctions of Lz are
1
Φm (ϕ) = √ eimϕ (28)
2π
The singlevaluedness of P hi restricts the values of m to integers, and, as shown before,
m takes values from −l to +l. The eigenfunctions of L2 are the spherical harmonics
L2 Ylm (θ, ϕ) = l(l + 1)~2 Ylm (θ, ϕ) (29)

3.3 Spin Angular omentum

Taking | +i and | −i as the eigenfunctions of Sz with eigenvalues ~/2 and −~/2 respec-
tively, we may represent
~
Ŝx =[| +ih− | + | −ih+ |] (30)
2
i~
Ŝx = [| −ih+ | − | +ih− |] (31)
2
~
Ŝx = [| +ih+ | − | −ih− |] (32)
2
Let | αi be an arbitrary state. If we rotate the coordinate system by an angle θ about an
axis n̂, the rotated state would become
| αiR = UR (n̂, θ) | αi
with  
Sn
UR (n̂, θ) = exp −i θ (33)
~
To see that this does indeed rotate the state, let us calculate the expectation value of the
operator Ŝx . Under rotation hŜx i = hα | Ŝx | αi →R hα | Ŝx | αiR , where,

R hα | Ŝx | αiR = hα | eiSθ/~ Ŝx e−iSθ/~ | αi

~
= hα | eiSθ/~ [| +ih− | + | −ih+ |]e−iSθ/~ | αi
2
~
= hα | eiθ/2 | +ih− | eiθ/2 + e−iθ/2 | −ih+ | e−iθ/2 | αi
2
~
= hα | (cos θ + i sin θ) | +ih− | +(cos θ − i sin θ) | −ih+ | e−iθ/2 | αi
2
~
= hα | (cos θŜx − sin θŜy ) | αi
2

13
Thus under rotation hSx i → hSx i cos θ − hSy i sin θ. One can, in a similar way, show
that hSy i → hSx i sin θ + hSy i cos θ. Since the rotation is about the z− axis, hSz remains
invariant. Note that while the expectation values are rotated by θ, the kets are rotated
by θ/2. We can write, inserting a complete set of states, | αi =| +ih+ || αi+ | −ih− || αi.
Thus
| αiR = e−iSz θ/2 | αi = e−iθ/2 | +ih+ || αi + e−iθ/2 | −ih− || αi
so that if θ = 2π, | αiR → − | αi.

14
 Quantum Mechanics - II
Angular Momentum - II : Addition of
Angular Momentum - Clebsch-Gordan
Coefficients
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 1, 2019

1 Introduction
Consider a spin-half particle. The state space of the particle is spanned by position kets
{| ~xi} and two dimensional spin space spanned by | ↑i and | ↓i. If the spin-orbit coupling
is weak, the Hilbert space is the product of the position space and the spin space, and is
spanned by
| ~x, ±i =| ~xi⊗ | ↑, ↓i
 
The rotation operator is still given by exp −iJ~ · n̂θ/~ , where J~ is given by

J~ = L
~ ⊗I⊕I⊗S
~

which is usually abbreviated as J~ = L

~ + S.
~ The rotation operator in the product space is
given by the product of the operators for the orbital and spin parts :
   
UR (n̂, θ) = exp −iL~ · n̂θ/~ exp −iS ~ · n̂θ/~

1
The total wavefunction is a a product of the space part and a spin part

ψα (~x) = ψ(~x)χα

where α =↑ or ↓. The wavefunction is a two component tensor

 
ψ↑ (~x)
ψ↓ (~x)

We have seen that the orbital angular momentum is described by the operator L2 and
Lz , while the spin operators by S 2 and Sz . The set of operators required to describe the
composite system is {L2 , Lz , S 2 , Sz }. Since the state space is a product of independent
states, we can write
| l, s, ml , ms i =| l, mm i⊗ | s, ms i
where

L2 | l, ml i = l(l + 1)~2 | l, ml i
Lz | l, ml i = ml ~ | l, ml i
S 2 | s, ms i = s(s + 1)~2 | s, ms i
Sz | s, ms i = ms ~ | s, ms i

Instead of considering spin and orbital angular momenta of a single particle, we could con-
sider more complex system consisting of two or more particles. We could, for instance,
talk about orbital momenta of two spinless particles or angular momenta of more com-
plex systems with many particles with different angular momenta. However, the basic
formulation remains the same as for adding two angular momenta. Let us consider two
angular momenta J1 and J2 . We define the total angular momenta of the system by

J~ = J~1 ⊗ I ⊕ I ⊗ J~2

abbreviated as
Jˆ = Jˆ1 + Jˆ2
[The hat or the vector signs (which is more commonly used) indicating the operator nature
of angular momentum will be frequently omitted. The commutation relations satisfied by

2
J1 and J2 are

[J1i , J1j ] = i~ijk J1k

[J2i , J2j ] = i~ijk J2k
[J1i , J2j ] = 0 (1)

Since the components of J1 commute with those of J2 , they can have common eigenstates.
We can choose, J12 , J1z , J22 and J2z to be a set of operators which have common eigenstates.
Let us denote the common eigenstates by | j1 , j2 ; m1 , m2 i ≡| j1 , m1 i | j2 , m2 i [ Note : This
notation is not standard, several books will denote this as | j1 , m1 , j2 , m2 i. We follow
Sakurai here.]. We then have

J12 | j1 , j2 ; m1 , m2 i = j1 (j1 + 1)~2 | j1 , j2 ; m1 , m2 i

J1z | j1 , j2 ; m1 , m2 i = m1 ~ | j1 , j2 ; m1 , m2 i
J22 | j1 , j2 ; m1 , m2 i = j2 (j2 + 1)~2 | j1 , j2 ; m1 , m2 i
J2z | j1 , j2 ; m1 , m2 i = m2 ~ | j1 , j2 ; m1 , m2 i

The dimension of the space to which J1 and J2 belong is (2j1 + 1)(2j2 + 1). The set of
states | j1 , j2 ; m1 , m2 i form a complete and orthonormal set
+j1 +j2
X X
| j1 , j2 ; m1 , m2 ihj1 , j2 ; m1 , m2 |= 1 (2)
m1 =−j1 m2 =−j2

hj1 , j2 ; m1 , m2 | j10 , j20 ; m01 , m02 i = δj1 ,j10 δj2 ,j20 δm1 ,m01 δm2 ,m02 (3)
As mentioned for the case of the orbital and spin angular momenta, the rotation operator
in this case is given by
! !
J~1 · n̂θ J~2 · n̂θ
U1R (n̂, θ) ⊗ U2R (n̂, θ) = exp −i exp −i
~ ~

As a consequence of (1), the components of the total angular momentum Jˆ satisfy

[Ji , Jj ] = i~ijk Jk (4)

which shows that Jˆ is an angular momentum operator. It is easy to check that J 2 com-
mutes with Jz , J12 and J22 . However, Jz does not commute with either J1z or J2z . As a re-
sult, it is possible to consider an alternate set of commuting operators, viz., {J 2 ,z , J12 , J22 }

3
which would describe the same space as did our old set {J12 , J22 , J1z , J2z }. We denote the
simultaneous eigenstates represented by this new set by | j1 , j2 ; j, mi. In terms of this
new set, we have

J 2 | j1 , j2 ; j, mi = j(j + 1)~2 | j1 , j2 ; j, mi (5)

Jz | j1 , j2 ; j, mi = m~ | j1 , j2 ; j, mi (6)

These kets are also eigenkets of J12 and J22 , though not of J1z and J2z . They satisfy the
completeness relation
j
X
| j1 , j2 ; j, mihj1 , j2 ; j, m |= 1 (7)
m=−j

They can be taken to be orthonormalized

hj1 , j2 ; , j, m | j10 , j20 ; j 0 , m0 i = δm,m0 δj,j 0 (8)

It is tacitly assumed that j1 and j2 in a given problem are given and fixed . We have not
yet found out what values j can take. However, the sum over j in (7) must be over all
values of j consistent with given values of j1 and j2 . Using the completeness property(2)
of the old set {| j1 , j2 ; m1 , m2 i}, we may express a member of the new set {| j1 , j2 ; j, mi}
as
j1 j2
X X
| j1 , j2 ; j, mi = | j1 , j2 ; m1 , m2 ihj1 , j2 , m1 , m2 | j1 , j2 ; j, mi (9)
m1 =−j1 m2 =−j2

The coefficients hj1 , j2 , m1 , m2 | j1 , j2 ; j, mi defined in (9) are called Clebsch-Gordan

(C-G)Coefficients.. The basis defined here as represented by the kets on the left hand
side of (9) will be also referred to as the Coupled Representation.

2 Properties of C-G Coefficients

1. The C-G coefficients hj1 , j2 , m1 , m2 | j1 , j2 ; j, mi are zero unless m = m1 + m2 . To
show this, note that Jz − J1z − J2z is a null operator,

hj1 , j2 , m1 , m2 | Jz − J1z − J2z | j1 , j2 ; j, mi = 0

4
 because Jz acts to the ket on its right giving m times the ket, while J1z − J2z acts
to the bra on the left giving m1 − m2 times the bra,

(m − m1 − m2 )hj1 , j2 , m1 , m2 | j1 , j2 ; j, mi = 0

which shows that of m 6= m1 + m2 , the C-G coefficient would be zero.

2. By convention, the C-G coefficients are taken to be real, so that

hj1 , j2 , m1 , m2 | j1 , j2 ; j, mi = hj1 , j2 ; jm | j1 , j2 ; m1 , m2 i

3. Orthonormality of C-G Coefficients : In the expression (8) given above, if we insert

a complete set given by (2) of old states, we get

hj1 , j2 ; , j, m | j10 , j20 ; j 0 , m0 i = δm,m0 δj,j 0

+j1 +j2
X X
hj1 , j2 ; j, m | j1 , j2 ; m1 , m2 ihj1 , j2 ; m1 , m2 | j10 , j20 ; j 0 , m0 i = δm,m0 δj,j 0
m1 =−j1 m2 =−j2
(10)

Substituting j = j 0 and m = m0 in the above, we get

X
| hj1 , j2 ; m1 , m2 | j1 , j2 ; j, mi |2 = 1 (11)
m1 ,m2

In a similar way may start with the orthonormality condition on the old basis set
(3) and insert the completeness condition (7) of the new basis set to obtain

+j
X X
| hj1 , j2 ; m1 , m2 | j1 , j2 ; j, mi |2 = 1 (12)
j m=−j

4. The C-G coefficients vanish unless

| j1 − j2 |≤ j ≤ j1 + j2 (13)

The inequality on the right is obvious because mmax

1 = j1 and mmax
2 = j2 . Hence
max
m = j1 + j2 . Since the maximum value of m is j, the right inequality follows

5
 and jmax = j1 + j2 .
The inequality on the left requires a bit of working out. We know that there are
(2j1 + 1)(2j2 + 1) number of states. For each value of j, there are 2j + 1 states.
Thus we must have
jmax
X
(2j + 1) = (2j1 = 1)(2j2 + 1)
j=jmin

Left hand side of above is an arithmetic series of finite number of terms. The sum
works out as follows :
jmax − jmin + 1
l.h.s. = (2jmax + 1 + 2jmin + 1)
2
= (jmax − jmin + 1)(jmax + Jmin + 1)
= (jmax + 1)2 − jmin
2

= (j1 + j2 + 1)2 − jmin

2

2
Equating the above to (2j1 + 1)(2j2 + 1), we get jmin = (j1 − j2 )2 , which gives

jmin =| j1 − j2 |

Thus the values of j satisfies

| j1 − j2 |≤ j ≤ j1 + j2 (14)

5. For a given j, the possible m values are −j ≤ m ≤ +j.

A notation, primarily used by the nuclear physicists is known as Wigner’s 3-j symbol and
is related to C-G coefficients as follows. While the C-G coefficients are for adding two
angular moments, the 3-j symbols are for addition of three angular momenta such that
their sum gives zero angular momentum state.
 
j1 −j2 +m
p j1 j2 j
hj1 , j2 ; m1 , m2 | j1 , j2 ; j, mi = (−1) 2j + 1 (15)
m1 m2 m

3 Calculation of Clebsch-Gordan Coefficients

In the two limiting cases, i.e., for m1 = j1 , m2 = j2 ; m = j1 + j2 and m1 = −j1 , m2 =
−j2 ; m = −j1 − j2 , the CG coefficients are 1. For the other cases we need to obtain

6
recursion relations. Note that

J± | j1 , j2 ; j, mi = (J1,± + J2,± ) | j1 , j2 ; j, mi
X
= hj1 , j2 ; m01 , m02 | j1 , j2 ; j, mi(J1,± + J2,± ) | j1 , j2 ; m01 , m02 i
m01 ,m02

Applying the ladder operator on both sides

p X
(j ∓ m)(j ± m + 1) | j1 , j2 ; j, m ± 1i = hj1 , j2 ; m01 , m02 | j1 , j2 ; j, mi
m01 ,m02
p
(j1 ∓ m01 )(j1 ± m01 + 1) | j1 , j2 ; m01 ± 1, m02 i
p 
(j2 ∓ m02 )(j2 ± m02 + 1) | j1 , j2 ; m01 , m02 ± 1i (16)

Multiply both sides of the above equation by hj1 , j2 ; m1 , m2 | and use orthogonality con-
dition. The term on the left gives a CG coefficient. The first term on the right is non-zero
only if m1 = m01 ± 1 and m2 = m02 while the second term is non-zero if m1 = m01 and
m2 = m02 ±1. Using these on the right, we get a relationship between three CG coefficients.
p
(j ∓ m)(j ± m1 + 1)hj1 , j2 ; m1 , m2 | j1 , j2 ; j, m ± 1i =
p
(j1 ∓ m1 + 1)(j1 ± m1 )hj1 , j2 ; m1 ∓ 1, m2 | j1 , j2 ; j, mi
p
+ (j2 ∓ m2 + 1)(j2 ± m2 )hj1 , j2 ; m1 , m2 ∓ 1 | j1 , j2 ; j, mi (17)

Note that the left there are CG coefficients which require m1 + m2 = m ± 1.

3.1 Examples of CG Coefficient Calculation

Example 1 - Adding two spin 1/2 angular momenta :
We will denote the spins by ŝ1 and ŝ2 and total spin by Ŝ. This could, for instance,
represent the case of the spin states of hydrogen atom wherein the electron and the proton
each have spin 1/2. Clearly, the spin angular moments of two different particles commute.
The total spin S can take values from s1 − s2 to s1 + s2 , i.e. 0 and 1. Corresponding
to s = 0, there is only one state with m = 0 while for s = 1, there are three states
with m = −1, 0 and +1. The former is called a singlet while the latter trio are known
as triplets. (s1 = 1/2 has two states and s2 = 1/2 also has two states, so that there are

7
 1 1
2 × 2 = 4 states). We note that the state | , ; 1, 1i in the representation | s1 , s2 , s, mi
2 2
1 1 1 1
is uniquely obtained from the state | , ; , i of | s1 , s2 , m1 , m2 i representation.
2 2 2 2
1 1 1 1 1 1
| , ; 1, 1i =| , ; , i
2 2 2 2 2 2
Apply
p J− on the left and (J1− + J2− ) on the right and use the formula J| j, mi =
(j + m)(j − m + 1)

1 1 1 1 1 1
J− | , ; 1, 1i = (J1− + J2− ) | , ; , i
2 2 2 2 2 2
√ 1 1 1 1 1 1 1 1 1 1
2| , ; 1, 0i =| , ; − , i+ | , ; , − i
2 2 2 2 2 2 2 2 2 2

Thus the Clebsch-Gordon coefficients are

h1/2, 1/2; 1/2, 1/2 | 1/2, 1/2, 1, 1i = 1

1
h1/2, 1/2; 1/2, −1/2 | 1/2, 1/2, 1, 0i = √
2
1
h1/2, 1/2; −1/2, 1/2 | 1/2, 1/2, 1, 0i = √
2
The coefficient for s = 1.m = −1 need not be calculated as it is obtained by symmetry
to be also equal to 1. For s = 0, there is only state with m = 0. This state is orthogonal
to the state | 1/2, 1/2, 1, 0i and is given by
1
| 1/2, 1/2, 0, 0i = √ (| 1/2, 1/2, 1/2, −1/2i− | 1/2, 1/2, −1/2, 1/2i)
2
Thus
1
h1/2, 1/2; 1/2, −1/2 | 1/2, 1/2, 1, 0i = √
2
1
h1/2, 1/2; −1/2, 1/2 | 1/2, 1/2, 1, 0i = − √
2

8
It is conventional to indicate the state with m = 1/2 as | ↑i or as α. The state with
m = −1/2 is then indicated as | ↓i or as β. The triplet states are then s = 1 :

m = +1 :| ↑↑i
1
m = 0 : √ [| ↑↓i+ | ↓↑i)
2
m = −1 :| ↓↓i

It may be noted that the triplets are symmetric with respect to the two spins. The singlet
state s = 0 is given by
1
√ [| ↑↓i− | ↓↑i)
2
which is antisymmetric under exchange of spins.
When the magnitudes of the two angular momenta are different, it is conventional to
choose the one with larger magnitude as the first spin and the other one as the second.
This convention has some repercussion in fixing the signs of Clebsch-Gordan coefficients,
which we will talk about in the next example.
Example 2: A Hydrogen atom is known to be in the state n = 3, l = 2. Find all the
values of the total angular momentum j and for each j, the eigenvalue of J 2 operator.
1 1 5 3
We have l = 2, s = 1/2. Thus allowed values of j are from 2 − to 2 + , i.e. , . The
2 2 2 2
eigenvalue of J 2 being j(j + 1)~2 , we have, for j = 5/2 the eigenvalue is (35/4)~2 and
(15/4)~2 respectively.
3 1
Example 3: For two spins s = 1/2 each, show that I + 2 Ŝ1 · Ŝ2 is a projection operator
4 ~
1 1
for S = 1 and I − 2 Ŝ1 · Ŝ2 is a projection operator for S = 0
4 ~
Solution:
Note
3 1 3 1
I + 2 Ŝ1 · Ŝ2 = I + 2 [S 2 − S12 − S22 ]
4 ~ 4 2~
3
For S = 1, S 2 has eigenvalue 1(1 + 1)~2 = 2~2 and S12 and S22 have eigenvalue ~2 each.
4
Thus we get for S = 1 this expression to have value 1 and for S = 0 it has value 0. Thus
the operator projects S = 1 state.
Example 4: Adding j1 = 1 with j2 = 1/2
In this case, in the j1 , j2 ; m1 , m2 representation there are 3 × 2 = 6 states. The resultant

9
 3 1
angular momentum which satisfies | j1 − j2 |≤ j ≤ j1 + j2 can take values and , the
2 2
former has 4 states and the latter 2, making a total of 6 states as before. We proceed as
follows. Start with the state having maximum j value and maximum possible m value
3 3
corresponding to this j. In this case it is j = and m = . This state is obtained
2 2
uniquely from j1 = 1, m1 = 1 and j2 = 1/2, m2 = 1/2. Thus

| 1, 1/2; 3/2, 3/2i =| 1, 1/2; 1, 1/2i

We apply J− p
on the ket on the left and J1− +J2− to the ket on the right, using the formula
J− | j, mi = (j + m)(j − m + 1) | j, m − 1i. We then get
√ √
3 | 1, 1/2; 3/2, 1/2i = 2 | 1, 1/2; 0, 1/2i+ | 1, 1/2; 1, −1/2i (18)

From this it follows that

r
2
h1, 1/2; 3/2, 1/2 | 1, 1/2; 0, 1/2i =
3
r
1
h1, 1/2; 3/2, 1/2 | 1, 1/2; 1, −1/2i =
3
The remaining coefficients belonging to the negative values of m are obtained by symme-
try. We now consider the j = 1/2 state with = ±1/2. Once again, we will only compute
m = 1/2 term. Note that the state | 1, 1/2; 1/2, 1/2i is orthogonal to the state with the
same m but j = 3/2. Thus this state is orthogonal to
r r
2 1
| 1, 1/2; 3/2, 1/2i = | 1, 1/2; 0, 1/2i + | 1, 1/2; 1, −1/2i
3 3
The state which is orthogonal to the state on the right is obviously
r r !
1 2
| 1, 1/2; 1/2, 1/2i = ± | 1, 1/2; 0, 1/2i − | 1, 1/2; 1, −1/2i
3 3

Thus, there is an ambiguity on the overall phase. In order to fix the sign, we use what
is known as Condon-Shortley sign convention according which the state with the
highest m of the larger component of the angular momentum that is being added is
assigned a positive sign. In case where j1 = j2 , as was the case in the previous example,

10
the first mentioned one, i.e. j1 will be taken to be the larger component for application
of this convention. Thus in this case the state with j1 = 1, m1 = 1 will be taken to be
positive. Thus we have
r r
2 1
| 1, 1/2; 1/2, 1/2i = | 1, 1/2; 1, −1/2i − | 1, 1/2; 0, 1/2i
3 3
This gives two Clebsch-Gordan coefficients as follows
r
2
h1, 1/2; 1/2, 1/2 | 1, 1/2; 1, −1/2i =
3
r
1
h1, 1/2; 1/2, 1/2 | 1, 1/2; 0, 1/2i = −
3

11
 Example 5: Adding j1 = 1 with j2 = 1

Here in the j1 , j2 , m1 , m2 basis, there are 3 × 3 = 9 members. In the coupled represen-

tation the possible angular momenta are j = 2, 1, 0 with respectively 5, 3 and 1 states,
making it 9, as expected. In this case we start with

| 1, 1; 2, 2i =| 1, 1; 1, 1i

where the coupled representation is on the left. we apply J− on the left and J1− + J2− on
the right. we get
p p p
(2 + 2)(2 − 2 + 1) | 1, 1; 2, 1i = (1 + 1)(1 − 1 + 1) | 1, 1; 0, 1i+ (1 + 1)(1 − 1 + 1) | 1, 1; 1, 0i

Thus r r
1 1
| 1, 1; 2, 1i = | 1, 1; 0, 1i + | 1, 1; 1, 0i (19)
2 2
Further application of J− = J1− + J2− gives

√ 1 √ √ 1 √ √
r r
6 | 1, 1, 2, 0i = ( 2 | 1, 1; −1, 1i + 2 | 1, 1, 0, 0i) + ( 2 | 1, 1; 0, 0i + 2 | 1, 1, 1, −1i)
2 2
√
r
1
| 1, 1, 2, 0i = [| 1, 1; 1, −1i + 2 | 1, 1, 0, 0i) + 2 | 1, 1; −1, 1i] (20)
6
The state with j = 1, m = 1 is orthogonal to the state (19). Using the sign convention
discussed above r r
1 1
| 1, 1; 1, 1i = | 1, 1; 1, 0i − | 1, 1; 0, 1i (21)
2 2
An application of J− = J1− + J2− on (21) gives
r r
1 1
| 1, 1; 1, 0i = | 1, 1; 1, −1i − | 1, 1; −1, 1i (22)
2 2
It may be noted that in the above state there is no contribution from m1 = m2 = 0 state
to m = 1 state.
Now the state | 1, 1; 0, 0i is orthogonal to both (20) and (22). Let the state be written as

| 1, 1; 0, 0i = a | 1, 1; 1, −1i + b | 1, 1; 0, 0i + c | 1, 1; −1, 1i

12
where a, b and c are constants to be determined. Since the state is orthogonal tio (22),
we have a = c. Orthogonality to (20) gives a + 2b + c = 0. Solving, we get b = −c. Thus
the state is
| 1, 1; 0, 0i = a[| 1, 1; 1, −1i− | 1, 1; 0, 0i+ | 1, 1; −1, 1i]
1
The constant a is determined to be √ by normalization of the state. Thus we get
3
1
| 1, 1; 0, 0i = √ [| 1, 1; 1, −1i− | 1, 1; 0, 0i+ | 1, 1; −1, 1i]
3
Collecting the above results together, we get the Clebsch-Gordan coefficients to be given
by
m = 2, 1

h1, 1; 2, 2 | 1, 1; 1, 1i = 1
1
h1, 1; 2, 1 | 1, 1; 1, 0i = √
2
1
h1, 1; 2, 1 | 1, 1; 0, 1i = √
2
1
h1, 1; 1, 1 | 1, 1; 1, 0i = √
2
1
h1, 1; 1, 1 | 1, 1; 0, 1i = − √
2

13
m = 0:
1
h1, 1; 2, 0 | 1, 1; 1, −1i = √
6
r
2
h1, 1; 2, 0 | 1, 1; 0, 0i =
3
1
h1, 1; 2, 0 | 1, 1; −1, 1i = √
6
1
h1, 1; 1, 0 | 1, 1; 1, −1i = √
2
1
h1, 1; 1, 0 | 1, 1; −1, 1i = − √
2
1
h1, 1; 0, 0 | 1, 1; 1, −1i = √
3
1
h1, 1; 0, 0 | 1, 1; 0, 0i = − √
3
1
h1, 1; 0, 0 | 1, 1; −1, 1i = √
3

14
 Quantum Mechanics - II
Angular Momentum - III : Wigner- Eckart
Theorem
Dipan Kumar Ghosh
Physics Department, Indian Institute of Technology Bombay
Powai, Mumbai 400076
September 2, 2019

1 Introduction
Wigner-Eckart Theorm deals with obtaining matrix elements of operators between states
of definite angular momentum. For a class of operators, known as “Tensor Operators”,
the effect of such operators on a state of given angular momentum is to act as if an angular
momentum is being added to the system.
Suppose a state | ψi transforms to the state | ψ 0 i under rotation:

| ψ 0 i = UR | ψi (1)

where U (R) is the operator for rotation which form a representation for SO(3) group (i.e.
it excludes rotation followed by inversion, det U = +1). If  is an operator, the “rotated
operator” Â0 is defined so that the expectation value of Â0 in the rotated states will be
equal to the expectation value of  in the original states of the system, i.e.

hψ 0 | Â0 | ψ 0 i = hψ | Â | ψi (2)

Using (1), we can write the above as

hψ | UR† Â0 UR | ψi = hψ | Â | ψi (3)

1
This implies
Â0 = UR ÂUR† (4)

2 Operator Transformation Under Rotation

In the following we will classify the operators according to the way they transform under
rotation. Consider first, a scalar operator. By definition, this is an operator which
remains invariant under rotation, so that
Â0 = UR ÂUR† = Â
i.e., the operator  commutes with the rotation operator UR . In particular, it commutes
with generators of infinitesimal rotation, and hence, with all the components of angular
momentum operator.
[A, Ji ] = 0
Example of such an operator is the Hamiltonian of an isolated system for which the
eigenstates of the Hamiltonian are also eigenstates of the angular momentum.
Next, let us consider vector operators, such as ~x, p~, L,~ S
~ etc. We know that, under
rotation, the components of a classical vector V~ transform as
X
Vi = Ri,j Vj
j

where R is the rotation matrix. For infinitesimal rotationj by an angle  about an axis n̂,
the transformed vector can be expressed as
V~ → V~ 0 = V~ + n̂ × V~ (5)
Under rotation, the state vector transforms as given by (1), where, for infinitesimal rota-
tion , the operator UR is given by
i
UR = 1 − n̂ · J~ (6)
~
We define an operator to be a vector operator, if the the expectation values of the com-
ponents of the operator transform like the components of a vector. Since the components
of the operator Ai , under rotation, becomes (cf. (4)) UR Ai UR† this implies
X
UR Ai UR† = Ri,j Aj (7)
j

2
where R is the rotation matrix. Written explicitly, it implies,
X
hψ 0 | Â | ψ 0 i = Ri,j hψ | Âj | ψi
j

Using (5) and (4), we have

   
i ~ i ~
1 + n̂ · J Â 1 − n̂ · J = Â + n̂ × Â
~ ~
Keeping terms to order , this gives
i ~ Â] = n̂ × Â
[n̂ · J,
~
which simplifies to
~ = i~n̂ × Â
[Â, n̂ · J] (8)
This equation is actually three equations. For the i− th component of Â, it gives
~ = i~[n̂ × Â]i
[Ai , n̂ · J]

Fix i to be x [for instance] and take n̂ to be x̂, ŷ and ẑ, in turn. We then get

[Ax , Jx ] = i~[x̂ × Â]x = 0

[Ax , Jy ] = i~[ŷ × Â]x = i~Az
[Ax , Jz ] = i~[ẑ × Â]x = −i~Ay

We can repeat the algebra, taking i = y and i = z. The commutation relations that we
get can be written compactly as

[Ai , Jj ] = i~ijk Ak (9)

We take (9) to be the definition of a vector operator.

~ = ~r × p satisfy
For instance the position operator ~r and angular momentum operator L
the commutation relation
[ri , Lj ] = i~ijk rk
and, similarly, for the momentum operator, we have,

[pi , Lj ] = i~ijk pk

3
Tensor Operators:
A classical tensor is defined as a generalization of a vector to a quantity which is described
by more than two indices. For instance, a tensor of rank 2 has 9 quantities Ti,j where
i = 1, 2, 3 and j = 1, 2, 3. Likewise, a tensor of rank 3 consists of 27 quantities Ti,j,k .
Under rotation, the components of a tensor mix and we have,
X
Ti,j = Ri,l Rj,m Tl,m
l,m

and, similarly X
Ti,j,k = Ri,l Rj,m Rk,n Tl,m,n
l,m,n

The simplest second rank tensor is a “dyadic” which is formed out of components of two
vectors A and B,
Ti,j = Ai Bj
However, such “cartesian tensors” are reducible in the sense that they can be divided into
distinct groups such that elements of a group only mix among themselves under rotation,
in the sense that they can be divided into distinct groups such that elements of a group
only mix among themselves under rotation. These groups are as follows:
1. Scalar: A tensor of rank zero having only one component
~·B
A ~
0
Ti,j = δi,j
3
which is just the usual definition of a scalar product, excepting for the factor of 1/3
(the reason for the factor becomes clear later.

2. An antisymmetric tensor of rank 1 (i.e. an axial (pseudo vector) with compo-

nents
1 Ai Bj − Aj Bi ~ × B)
~ k
Ti,j = = ijk (A
2
3. A symmetric, traceless tensor with 5 independent components

Ai Bj + Aj Bi A~·B~
2
Ti,j = − δi,j
2 3
(A 3 × 3 symmetric tensor has 6 independent components (3 along diagonal and 3
off diagonal). To reduce the number of independent components by 1, we put in the

4
 constraint of the matrix becoming traceless, which explains the factor of 1/3 in the
definition of scalar.
With these definition, it is easy to check that
0 1 2
Ai Bj = Ti,j + Ti,j + Ti,j
We note that the three groups, with multiplicities of 1, 3 and 5 respectively, are precisely
the same as we found for the number of states having l = 0, 1 and 2 respectively. Further, it
can be shown, by expressing the cartesian tensors in a spherical basis, that the components
transform like spherical harmonics.

3 Irreducible Operators in a Spherical Basis

The form of the scalar operator does not change on change of a basis. Let us see how
a vector operator change under change of basis. In order to see it, let us express the
components of a position vector in terms of spherical harmonics. We recall that the
expression for the spherical harmonics for l = 1 are given by
r
3
Y1,0 = cos θ
4π
r
3 iφ
Y1,1 = − e sin θ
8π
r
3 −iφ
Y1,−1 = e sin θ (10)
8π
Using these, we can write
x = r sin θ cos φ
1
= r sin θ(eiφ + e−iφ )
2 r
r 8π
=− (Y1,1 − Y1,−1 ) (11)
2 3
In a similar way, we have
r
r 8π
y= (Y1,1 + Y1,−1 ) (12)
2i 3
r
4π
z= Y1,0 (13)
3

5
Thus, we can express the spherical harmonics in terms of the components of the position
operator.
r
3 z
Y1,0 =
4π r
r
3 x + iy
Y1,1 = − √
4π 2r
r
3 x − iy
Y1,−1 = √ (14)
4π 2r
Thus the spherical components of a position vector can be defined,( ignoring the constants
x + iy x − iy
and taking r = 1 as r0 = z, r1 = − √ and r−1 = + √ . Taking this as a guide, we
2 2
can express the spherical components of a vector (i.e. a tensor of rank 1) A in terms its
cartesian components:
(1)
A0 = Az
(1) Ax + iAy
A+1 = − √
2
(1) Ax − iAy
A−1 = √ (15)
2
Using (9) and (15), we can obtain the commutator of these operators in a spherical basis
with the angular momentum operators.
(1)
[Jz , A0 ] = [Jz , Az ] = 0
(1) 1 (1)
[Jz , A+1 ] = √ [Jz , −Ax − iAy ] = i~(−Ay + iAx ) = ~A+1
2
(1) 1 (1)
[Jz , A−1 ] = √ [Jz , Ax − iAy ] = i~(Ay + iAx ) = −~A−1 (16)
2
Similarly,
(1)
[J+ , A0 ] = [Jx + iJy , Az ]
√ (1)
= (i~)(−Ay + iAx ) = −~(Ax + iAy ) = 2~A1 (17)

(1)
[J− , A0 ] = [Jx − iJy , Az ]
√ (1)
= (i~)(−Ay − iAx ) = −~(Ax − iAy ) = − 2~A−1 (18)

6
 (1) (1)
[J+ , A+1 ] = [J− , A−1 ] = 0
(1)
√ (1)
[J+ , A−1 ] = 2~A0 (19)
√
[It may be noted that the appearance of the factor of 2 in the above commutation
relation is because of the fact that the angular momentum raising and lowering operators
√
themselves are defined without the 2 factor.] The set of commutation relations above
can be generalised by taking the rank to be k and its components as q,

[Jz , A(k) (k)

q ] = ~qAq (20)
(k)
p
[J± , A(k)
q ] = ~ k(k + 1) − q(q ± 1)Aq±1 (21)

3.1 Example: Irreducible tensor of rank 2

Express the components of second rank tensor in the spherical basis in terms of spherical
harmonics.
The irreducible spherical tensors of rank 2 can be obtained from the product of two
spherical tensors of rank 1 as follows:
(2) (1) (1)
(A(1) ⊗ B (1) )2 = A+1 B+1
(2) 1 (1) (1) (1) (1)
(A(1) ⊗ B (1) )1 = √ (A+1 B0 + A0 B+1 )
2
(2) 1 (1) (1) (1) (1) (1) (1)
(A(1) ⊗ B (1) )0 = √ (A+1 B−1 + 2A0 B0 + A−1 B+1 )
6
(2) 1 (1) (1) (1) (1)
(A(1) ⊗ B (1) )−1 = √ (A−1 B0 + A0 B−1 )
2
(1) (1) (2) (1) (1)
(A ⊗ B )−2 = A−1 B−1 (22)

7
Consider forming a second rank tensor using the components of the position vector the
way we did for the first rank tensor.

(2) 1 1
T+2 = (x + iy)2 = (x2 − y 2 + 2ixy)
2 2 r
1 8π
= r2 sin2 θe2iφ = r2 Y2,2
2 15
(2) 1
T+1 = √ (2r+1 r0 ) = −z(x + iy)
2
r
iφ 2 8π
= − sin θ cos θe = r Y2,1
15
(2) 1
T0 = √ (2r+1 r−1 + 2r0 r0 )
6
1
= √ (−x2 − y 2 + 2z 2 )
6
r
8π
= r2 Y2,0 (23)
15
Thus the five components transform like the spherical harmonics for l = 2.

4 Wigner - Eckart Theorem

Wigner - Eckart theorem states that the matrix elements of irreducible tensor operators
with respect to angular momentum eigenstates can be factored and written as a product
of a term which does not depend on the angular momentum projections (i.e. on m values)
and another which is just the Clebsch Gordan coefficient:

hα0 , j 0 , m0 | Tq(k) | α, j, mi = hα0 , j 0 || T (k) || α, jihj, k; m, q | j, k; j 0 , m0 i (24)

where α, α0 are other quantum numbers of the problem. The first factor is known as the
reduced matrix element. In the following, we give an intuitive proof of the theorem.
Since the states are eigenstates of angular momentum operators, we have

hk, q | Jz | k, qi = ~qhk, q 0 | k, qi

8
from which it follows, using (21),
+k
X +k
X
(k) (k)
Tq0 hk, q | Jz | k, qi = Tq0 ~qδq,q0 = ~qTq(k)
q 0 =−k q 0 =−k

= [Jz , Tq(k) ] (25)

Similarly, the matrix elements of J± are given by

p
hk, q 0 | J± | k, qi = ~ (k ∓ q)(k ± q + 1)δq0 ,q±1 (26)

which gives
+k
X (k)
Tq0 hk, q 0 | J± | k, qi = [J± , Tq(k) ] (27)
q 0 =−k

Using (24), we get on taking matrix elements between arbitrary set of states,

hα0 , j 0 , m0 | [Jz , Tq(k) ] − ~Tq(k) | α, j, mi = 0

Using the fact the states on either side are eigenstates of Jz , we get

(m0 − m − q)hα0 , j 0 , m0 | Tq(k) | α, j, mi = 0

(k)
which indicates that hα0 , j 0 , m0 | Tq | α, j, mi = 0 unless m0 = m + q, which is a property
of the Clebsch-Gordan coefficient hj, k; j 0 , m0 | j, k; m, qi. Using (26), we get
(k)
p
hα0 , j 0 , m0 | [J± , Tq(k) ] − ~ (k ∓ q)(k ± q + 1)Tq±1 | α, j, mi = 0

Expanding the commutator and using the operators J± on the states, we get
p
(j 0 ± m0 )(j 0 ∓ m0 + 1)hα0 , j 0 , m0 ∓ 1 | Tq(k) | α, j, mi
(k)
p
= (k ∓ q)(k ± q + 1)hα0 , j 0 , m0 | Tq±1 | α, j, mi
p
+ (j ∓ m)(j ± m + 1)hα0 , j 0 , m0 | Tq(k) | α, j, m ± 1i (28)

which is identical to the recursion relation between the Clebsch Gordan coefficients
observed earlier (cf. eqns. (21) and (22) of the notes on angular momentum addition),

9
which we reproduce for convinence. In addition, we have used the reality of the CG
coefficients to interchange the order of the two representations:
p
(j ∓ m)(j ± m + 1)hj1 , j2 ; j, m ± 1 | j1 , j2 ; m1 , m2 i
p
= (j1 ± m1 )(j1 ∓ m1 + 1)hj1 , j2 ; j, m | j1 , j2 ; m1 ∓ 1, m2 i
p
= (j2 ± m2 )(j2 ∓ m2 + 1)hj1 , j2 ; j, m | j1 , j2 ; m1 , m2 ∓ 1i (29)
(k)
The equations (28) and (29) are identical if one realizes that the action of Tq on the
ket to its right is equivalent to adding to | j, mi a state with angular momentum | k, qi.
The equivalence between the two equations becomes apparent if one makes the following
identification:
Eqn. (28) Eqn. (29)
j0 j
j j1
k j2
m0 m
m m1
q m2

Both these sets of equations are first order linear equations with identical coefficients. If
we have two sets of equations X
ai,j xj = 0
j

and
ai,j yj = 0
we can solve for the ratio of any two quantities
xi yi
= =c
xj yj
(k)
where c is a proportionality factor. Thus the matrix elements of Tq between two angular
momentum states is proportional to the Clebsch Gordan coefficients and the constant of
proportionality is independent of m, m0 and q. This completes the proof of the Wigner-
Eckart theorem.

10
5 Examples
Example 1 :
1
Relate the matrix elements hn0 , l0 , m0 | ∓ √ (x ± iy) | n, l, mi with hn0 , l0 , m0 | z | n, l, mi
2
, where n, l, m are the quantum numbers associated with hydrogen atom wavefunctions.
Solution:
1 1
Note that ∓ √ (x ± iy) = T±1 is a tensor of rank 1 in the spherical basis while z = T01 is
2
the third component of the same vector. Thus the reduced matrix element in each case
is hn0 , l0 | |T 1 | | n, li. Thus the matrix elements would be proportional to the Clebsch-
Gordan coefficients hl0 , m0 | l, 1; m, qi and hl0 , m0 | l, 1; m, 0i respectively.
In both cases, in order that the matrix elements are non-zero, we must have, | l − 1 |≤
l0 ≤ l + 1. However, for the former case we require m0 = m ± 1 while in the later case
m0 = m. [In case l = l0 = 1; m = m0 = 0, see these C-G coefficients calculated explicitly
in the lecture on addition of angular momentum j1 = j2 = 1.]
Example 2:
Given α = hl = 2, m = +2 | xy | l = 0, m = 0i, obtain in terms of α, the matrix elements
of the operator hl = 2, m | Ô | l0 = 0, m0 = 0i, where Ô is xz, yz, z 2 and x2 .
Solution:
Since Wigner Eckart theorem is applicable to spherical tensors, we will express the op-
erators in terms of components of spherical tensors. A rank 2 Cartesian tensor, like the
1
ones given in this problem must first be expressed in terms of T00 = (x2 + y 2 + z 2 ) and
3
Tk2 where the components of T 2 are as given in the text:
1
T22 = (x2 + 2ixy − y 2 )
2
2
T1 = −z(z + iy)
1
T02 = √ (−x2 − y 2 + 2z 2 )
6
2
T−1 = +z(z − iy)
2 1
T−2 = (x2 − 2ixy − y 2 )
2

11
It follows that
T22 − T−22
xy =
2i
T−1 − T12
2
xz =
2
i(T12 + T−12
)
yz =
2
The operators z 2 and x2 need a bit of working out. We have
r
1 1 1 3
T02 = √ (−x2 −y 2 +2z 2 ) = √ (−x2 −y 2 −z 2 +3z 2 ) = √ (−3T00 +3z 2 ) = (−T00 +z 2 )
6 6 6 2
where we have used T00 = (x2 + y 2 + z 2 )/3. Hence
r
2 2
z2 = T + T00
3 0
We have,

T22 + T−2
2
= x2 − y 2 = 2x2 − (x2 + y 2 ) = 2x2 + z 2 − (x2 + y 2 + z 2 ) = 2x2 + z 2 − 3T00

Substituting for z 2 we get

r
2 2
T22 + 2
T−2 2
= 2x + T + T00 − 3T00
3 0
which gives
1 1
x2 = (T22 + T−2
2
) − √ T02 + T00
2 6
Given,
T22 − T−22
α = h2, 2 | xy | 0, 0i = h2, 2 | | 0, 0i
2i
1
= h2 | | T 2 || | 0i[h2, 2 | 2, 0; 2, 0i − h2, 2 | 2, 0; −2, 0i
2i
1
= h2 || T 2 || 0i
2i
where we have used Wigner-Eckart theorem and the fact that h2, 2 | 2, 0; 2, 0i = 1 and
h2, 2 | 2, 0; −2, 0i = 0 as the latter does not satisfy m0 = m + q. The notation used is

12
h2, 2 | xy | 0, 0i ≡ hl0 = 2, m0 = 2 | xy | l = 0, m = 0i. Thus the reduced matrix element
is given by
h2 || T 2 || 0i = 2iα
We now come to evaluation of the matrix elements, which boils down to calculation of
Clebsch-Gordon coefficients.
1 2
h2, m | xz | 0, 0i = [h2, m | T−1 − T12 | 0, 0i]
2
1
= h2 || T 2 || 0i[h2, m | 2, 0; 0, −1i − h2, m | 2, 0; 0, −1i]
2
= (iα)[h2, m | 2, 0; 0, −1i − h2, m | 2, 0; 0, −1i]

The first CG coefficient is non-zero, only if m = −1 while the second CG coefficient is

non-zero only if m = 1. In both cases, the coefficient is 1. We thus have

h2, −1 | xz | 0, 0i = iα
h2, 1 | xz | 0, 0i = −iα

All other elements are zero. In a similar way, we can show that the non-zero matrix
elements of yz are

h2, −1 | yz | 0, 0i = α
h2, 1 | yz | 0, 0i = α

We now calculate the matrix elements of z 2 .

r
2 2
h2, m | z | 0, 0i = h2, m | T02 | 0, 0i + h2, m | T00 | 0, 0i
3
r
2 2
= h2 || T || 0i[ h2, m | 2, 0; 0, 0i + h2, m | 0, 0; 0, 0i]
3
r
2
= (iα)[ h2, m | 2, 0; 0, 0i + h2, m | 0, 0; 0, 0i]
3
The CG coefficient in the second term vanishes because 0 and 0 do not add up to 2. For
the first CG coefficient to vanish we must have m = 0. Thus the only non-zero matrix
element of z 2 is r
2 2 4
h2, 0 | z | 0, 0i = (2iα) = √ iα
3 6

13
 1 1
Finally, let us calculate the matrix element of x2 = (T22 + T−2
2
) − √ T02 + T00 . We have
2 6
1 1
h2, 0 | x2 | 0, 0i = h2, m | (T22 + T−2 2
) | 0, 0i − √ h2, m | T02 | 0, 0i + h2, m | T00 | 0, 0i
2 6
1 1
= h2 || T 2 || 0i[ h2, m | 2, 0; 2, 0i + h2, m | 2, 0; −2, 0i
2 2
1
− √ h2, m | 2, 0; 0, 0i + h2, m | 0, 0; 0, 0i]
6
The last term is zero because of angular momentum addition law as 0 and 0 do not add
up to 2. The non-zero matrix elements are given by the Clebsch-Gordon coefficients of
the remaining three terms (in each case it is 1). we get

h2, 2 | x2 | 0, 0i = iα
h2, −2 | x2 | 0, 0i = iα
r
1 2
h2, 0 | x2 | 0, 0i = − √ (2iα) = − iα
6 3
Example3:
In nuclear physics, a quantity known as “isospin” can be represented by a set of operators
{I, I3 } which satisfies the same algebra as that of angular momentum. Proton and neutron
are identical particles (having I = 1/2) with respect to the strong nuclear force defined
1 1
by I3 = , and I3 = − respectively. Isospins couple among themselves but not with
2 2
nuclear angular momentum. In string interaction, isospin is conserved, i.e., I 2 , I3 remain
constant. The isospin is conserved, i.e., I 2 , I3 remain constant. The isospins of some
other particles are: I3 = +1, 0, −1 for π + , π 0 , π − respectively, ρ mesons: I3 = +1, 0, −1
for ρ+ , ρ0 , ρ− respectively, ∆ particles: I3 = +3/2, +1/2, −1/2, −3/2 for ∆++ , ∆+ , ∆0 , ∆−
respectively.
Determine the ratio of the decay rates of the following:
ρ0 → π 0 π 0
ρ0 → π + π −
∆+ → pπ 0
∆+ → nπ +
Solution:
Since isospin is conserved in strong interaction, v must be a scalar operator and the decay

14
amplitudes must then be proportional to the CG coefficients

hi | V | f i ∝ hi | f ihi k V k f i

For ρ0 → π 0 π 0 , the CG coefficients is h1, 0 | 1, 1; 0, 0i = 0 because

1
| 1, 0i = √ [| 1, 1i | 1, −1i− | 1, −1i | 1, 1i]
2
Thus the first decay rate is zero.
3 1
For ∆ → pπ 0 the state | ∆+ i =| , i By calculation of the Clebsch Gordon coefficients,
2 2
it can be seen that
r
1 2
| 3/2, 1/2i = √ | 1/2, −1/2i⊗ | 1, 1i + | 1/2, 1/2i | 1, 0i
3 3

Thus the second ratio is √ √

2/ 3
[ √ ]2 = 2
1/ 3
Example 4:
Write xy, xz and x2 − y 2 as components of a second rank tensor. The quadrupole moment
Q is given by
Q = ehα, j, m = j | (3z 2 − r2 ) | α, j, m = ji
Determine matrix element

ehα, j, m0 | (x2 − y 2 ) | α, j, m = ji

where m0 takes allowed values, in terms of Q and the Clebsch Gordon coefficients.
Solution: We have
(2) 1 1
T±2 = (x ± iy)2 = (x2 − y 2 ± 2ixy)
2
√ 2
(2)
T±1 = 2r± z = ∓z(x ± iy) = ∓xz − iyz
(2) 1 1
T0 = √ (2r0 r0 + 2r+ r− ) = √ (2z 2 − x2 − y 2 )
6 6

15
Using these we get,

x2 − y 2 = T2 + T−2
i
xy = − (T2 − T−2 )
2
1
xz = − (T1 − T−1 )
2
i
yz = (T1 + T−1 )
2
Thus √
2z 2 − x2 − y 2 = 3z 2 − r2 = 6T02
Now
√
Q= 6ehα, j, m = j | T02 | α, j, m = ji
√
= 6ehα, j k T 2 k α, ji × hj, 2; j, 0 | j, 2; j, ji

ehα, j, m0 | x2 − y 2 | α, j, m = ji = ehα, j, m0 | T22 − T−2

2
| α, j, m = ji
However, since m0 ≤ j, the matrix element of T22 gives zero, and the remaining mateix
element is as follows.

ehα, j, m0 | T−2
2
| α, j, m = ji = −ehα, j k T 2 k α, ji × hj, 2; j, m0 | j, 2; j, −2i
Q hj, 2; j, m | j, 2; j, −2i
= −√
6 hj, 2; j, 0 | j, 2; j, ji
Example 5 :
Show that S ~ · T~ can be expressed in terms of the spherical components as
P+1 q 1 1
q=−1 (−1) Sq T−q .
Solution
Expanding the given expression we have
+1
X
1
(−1)q Sq1 T−q = −S11 T−1
1
+ S01 T01 − S−1
1
T11
q=−1

Substitute the spherical components in terms of the Cartesian components, e.g.

1 Tx ± iTy
T±1 =∓ √ ; T01 = Tz
2

16
to obtain the result.
Example 6: Show that the matrix elements of a scalar operator S00 in the angular
momentum states hj 0 , m0 | S00 | j, mi vanishes unless j 0 = j and m0 = m.
Solution:
We have,
hj 0 , m0 | S00 | j, mi = hj 0 || S 0 || jihj 0 , m0 | j, 0; m, 0i
The Clebsch -Gordan coefficient is zero unless j 0 = j ⊕ 0 = j and m0 = m + 0 = m.

17
 Quantum Mechanics - II
Angular Momentum - II : Symmetry in
Physics
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 16, 2019

1 Introduction
We have been acquainted with the concept of symmetry in classical mechanics and its
relationship with conservation laws. Understanding symmetry helps us in making sense
out of a clutter of experimental data. The relationship between symmetry and conserva-
tion laws was demonstrated by the famous Noether’s theorem, which states that if the
classical Lagrangian of a physical system is left unchanged by a continuous symmetry
transformation, a physical quantity would then become conserved in time. For instance,
homogeneity of space under translation implies that the physical laws must be invariant
under such translation. This gives rise to conservation of linear momentum. Likewise,
isotropy of space would require that the physical laws are invariant under rotation. This
would result in conservation of angular momentum. A somewhat less obvious symmetry is
the connection between time translation and conservation of energy. If the Lagrangian of
the system does not explicitly depend upon time and the potential is velocity independent,
conservation of energy would follow. These symmetries arise due to inherent structure
of space time and are generally referred to as geometrical symmetries. There is a class
of symmetry which has its origin in the nature of forces between interacting bodies. For
instance, there are accidental degeneracies in the spectrum of harmonic oscillator or the

1
hydrogen atom, where the energies are independent of the angular momentum quantum
numbers. The origin of such degeneracies can be traced to a symmetry higher than O(3)
symmetry associated with geometry. The symmetry in such cases, which are relatively
rare, are called dynamical symmetry. In this lecture, we will look into the extension of
these ideas to quantum mechanics. As has been pointed out earlier, there are two corre-
spondence which enables us to map the classical prescriptions to the quantum mechanical
ones. The classical Poisson bracket is replaced in quantum mechanics by the commutator
of the corresponding operators (up to a factor i~) and the canonical transformations of the
phase space is replaced by unitary transformations in the Hilbert space. The conserved
dynamical quantities arising out of the continuous symmetries of the classical Lagrangian,
results, in quantum mechanics from the corresponding symmetry of the Hamiltonian and
yield a constant of motion of a hermitian operator (corresponding to the physical observ-
able).

2 Classification of Symmetry
As in classical mechanics, we may classify transformation as active ( involving, for in-
stance, the physical position of a rigid body on rotation) or passive (which is merely a
transformation of the coordinate axes). In quantum mechanical analogue, we represent
active transformation by physically changing the state of the system by a unitary operator,
| ψi →| ψ 0 i = Û | ψi (1)
Alternatively, we may provide a passive view of transformation by keeping the state
unchanged but transforming the operators corresponding to the physical observables. An
expression for such “rotated operator” is obtained by requiring that the expectation value
of the operator  remains the same in both the pictures, i.e. hψ 0 | Â0 | ψi ≡ hψ |  | ψi,
which gives
hψ | U † Â0 Û | ψi ≡ hψ | Â | ψi (2)
resulting in
Â0 = U ÂU † (3)
We know that the square of the scalar product | hψ | φi |2 gives the probability that a
measurement made on the state | ψi collapses the state to the state | φi. If a transforma-
tion Û takes a system from the state | ψi to | ψ 0 i and a state | φi to the state | φ0 i, then

2
the result of such a measurement would be the same whether the measurement was done
on the unprimed system or on the primed system. This implies
| hψ 0 | φ0 i |2 =| hψ | φi |2 =| hψ | U † U | φi |2
which implies
(
hψ | φi U is unitary
hψ | U † U | φi =
hφ | ψi U is anti − unitary
We define an anti-unitary operator Ũ by the following properties :
hŨ ψ | Ũ φi = hψ | φi (4)
The operator is linear but has different consequence when acting on a complex scalar
Ũ [| ψi+ | φi] = Ũ | ψi + Ũ | φi (5)
∗
Ũ c | ψi = c Ũ | ψi (6)
We will have more to say about such operators when we deal with time reversal and
charge conjugation symmetries.
From a different perspective, symmetries may be continuous or discrete. Continuous
symmetry, as the name suggests is the symmetry which can be built continuously from
identity by means of infinitesimal transformations. As such transformations must contain
the identity element of the group, continuous transformations are given by unitary opera-
tors. We are aware from Noether’s theorem of classical mechanics the intimate connection
between continuous symmetry and conservation of a physical quantity. This is also true
in quantum mechanics; the difference being that instead of a Lagrangian approach to
symmetry, we need to take a Hamiltonian approach. Space translation and rotations are
examples of such continuous transformations. There are symmetries which cannot be
built up by means of infinitesimal transformations starting with identity. Examples of
such discrete transformations are space inversion or reflection.
Consider systems for which an observable A corresponding to the hermitian operator Â
is left invariant under a continuous unitary transformation Û , i.e. U ÂU † = Â. The
transformation being continuous, may be built up from its infinitesimal generator G, i.e.
i
Û = 1 − Ĝ, where  is a real parameter and ~ has been introduced for convenience.
~
Note that
i
Û −1 = 1 + Ĝ = U †
~
3
 i
Since U † = 1 + Ĝ† , unitarity of Û , implies G† = G, i.e. Ĝ is a hermitian operator.
~
Symmetry implies that the system remains invariant under such an operation. Suppose
under the symmetry operation U , a state | ψi →| ψ 0 i and | phii →| φ0 i. If the time
development of the system is governed by Hamiltonian H, then we must have

hφ0 | H | ψ 0 i = hφ | H | ψi

Substituting | ψ 0 i = U | ψi and | φ0 i = U | φi, we get

hU φ | H | U ψi = hφ | H | ψi

which implies
hφ | U † HU | ψi = hφ | H | ψi
Since the above is true fro arbitrary states which are left invariant under the symmetry
operation, we must have
U † HU = H =⇒ [U, H] = 0 (7)
Since U is given by its infinitesimal generator Ĝ defined above, it implies [H, G] = 0.
Ig Ĝ is taken to be independent of time, we get, using Heisenberg’s equation of motion
dG
= [G, H] = 0 which implies that Ĝ is a constant of motion. Thus the symmetry
dt
generated by G leads to conservation of G. Since U commutes with the hamiltonian, it
has simultaneous eigenstates with it. Suppose H | En i = En | En i. Since U is a symmetry
operation, U | En i is also an energy eigenstate with the same energy, as,

H(U | En i) = U H | En i = En (U | En i)

However, the state U | En i need not be identical to the state | En i. In such a situation,
the energy spectrum is said to have degeneracy.

2.1 Translational Symmetry

2.1.1 Space Translation and Conservation of Momentum
Consider eigenkets of the position operator x̂. (Here we consider one dimensional trans-
lation; extension to the three dimensions in straightforward)

x̂ | xi = x | xi (8)

4
Let T (a) be the translational operator, whose action on | xi gives rise to the ket | x + ai.
Here a is a real parameter, independent of x. The effect of the translation operator on
the position operator is given by T (a)x̂T (a)† . Thus we have

T (a)x̂T (a)† | xi = (x + a) | xi

Using the infinite generator of translation, we have

   
ia ia
[ 1 − G x̂ 1 − G ] | xi = (x + a) | xi
~ ~
Expanding and using (8) we get
ia
− (Ĝx̂ − x̂Ĝ) = a =⇒ [Ĝ, x̂] = i~
~
Comparing this with the commutator [x̂, p̂] = i~, we conclude Ĝ = −p̂. Thus the in-
ia
finitesimal generator for translation by a is 1 + p. For finite translation, this gives
~
iap̂
G(a) = exp(i ) (9)
~
Three dimensional translation is given by
i~a · p̂
G(~a) = exp(i )
~
In a similar way one can show that the momentum translation operator is given by
i~p0 · r̂
G(~p0 ) = exp(i )
~
[In the active transformation, the same result can be derived by considering the action of
the translation operator on the wavefunction ψ(x),

T (a)ψ(x) = ψ(x + a)

We may expand ψ(x + a) in a Taylor series

dψ a2 d2 ψ
ψ(x + a) = ψ(x) + a + + ...
dx 2! dx2
dp
Identifying p = −i~ , the result follows.]
dx
5
2.1.2 Time Translation
The time translation is defined in an analogous way1 . Time translation symmetry is
understood in the following way. Time translation invariance means that the laws of
physics are unchanged if all the events are shifted by a common time interval τ , i.e.,
physical laws should not depend upon the origin chosen for time. We may formally define
it by saying that if the state of system at time t is given by | ψ(t)i then, there exists a
solution | ψ 0 (t)i of the quantum mechanical equation of motion which is equal to (up to
an uninteresting multiplicative phase) the previous solution at time t + τ , i.e.

| ψ 0 (t)i = eif (t,τ ) | ψ(t + τ )i

Here τ is a fixed real parameter having the dimension of time by which the two time
intervals are connected. Thus, there should be an operator U (τ ) which, acting on the
state | ψ(t)i would generate the state the state of the system at time t + τ . The form of
U is analogous to the way we defined generator of space translation. We postulate
 
iHτ
U (τ ) = exp − (10)
~

The action of U (τ ) is given by

U (τ ) | ψ(t)i =| ψ(t + τ )i (11)

Setting t = 0 in the above equation, we get

 
iHτ
U (τ ) | ψ(0)i = exp − | ψ(0)i = ψ(τ )
~

As τ is arbitrary, we would then have, for any time t,

 
iHt
| ψ(t)i = exp − | ψ(0)i (12)
~

Note that since τ is a fixed parameter, [U, H] = 0. Starting with the equation for
U | ψi, we have
∂
i~ (U | ψi) = H(U | ψi) = U H | ψi
∂t
1
: Lectures on Quantum Mechanics, Steven Weinberg, Cambridge, 2013

6
which gives
∂
i~ | ψ(t + τ )i = H | ψ(t + τ )i
∂t
Thus the time translated state satisfies the Schrödinger equation.

We have seen that in the Heisenberg picture, the time dependence of an operator Â
is given by    
Ht Ht
AH (t) = exp i ÂS exp −i
~ ~
For the particular case of the operator  being the Hamiltonian Ĥ itself, this would imply
that the form of the Hamiltonian remains the same in both the pictures.
Symmetry principle implies that if an observer sees a state | ψ(t)i evolving as per (12),
the another observer must see the state U | ψ(t)i evolving by the same physical equation,
where
U | ψ(t)i = exp(−iHt/~)U ψ(0) (13)
Equations (12) and (13) will be consistent if we have
   
Ht Ht
exp −i U = U exp −i
~ ~

which requires U to be a linear operator so that

U −1 HU = H

the Hamiltonian must be invariant under the symmetry transformation, For infinitesimal
generator G of U , as we have seen earlier, this gives rise to

[H, G] = 0

The above requires U to be unitary. For anti-unitary operators, because of the presence
of the complex number i, this would give rise to U † HU = −H. This means, for every
energy eigenstate | ψi with eigenvalue E, there would correspond an eigenstate U | ψi
with energy −E. This would make the spectrum of the energy unbounded from below
resulting in an unstable ground state, since we could choose an eigenstate with energy
as large as we desire and there would correspond a state of negative energy of an equal
magnitude.

7
2.1.3 Rotational Symmetry
In our discussion on SO(3) group, we have extensively discussed the subject of rotational
symmetry. We briefly touch upon it again for completeness. Consider rotation about a
fixed axis, say z-axis, by an angle δϕ. Taking δϕ ~ to be a vector of magnitude δϕ and
~ × ~r. Thus the
direction along the axis of rotation, the position vector ~r → ~r0 = ~r + δϕ
position vector changes by δr~ = δϕ~ ×~r. In a similar manner, the momentum vector would
change by δp~ = δϕ
~ × p~.
Let us write the generator of rotation as Ĝ The unitary operator for rotation is then given
~ · Ĝ
δϕ
by Û = exp(−i ), where Ĝ has been shown to be hermitian before. For infinitesimal
~
rotation, we have
~ · Ĝ
δϕ
Û = 1 − i
~
The operators are transformed as  →  = U ÂÛ † . Taking  to be the position operator
0

r̂, we have ! !
~ · Ĝ
δϕ ~ · Ĝ
δϕ
~ × ~r = 1 − i
~r + δϕ ~r 1 + i
~ ~
Taking the i−th component of both sides and using i, j, k as an ordered triad
! !
iX iX
ri + (δϕ)j rk − (δϕ)k rj = 1 − δϕm Gm ri 1 + δϕm Gm
~ m ~ m
" #
i X
(δϕ)j rk − (δϕ)k rj = − δϕm Gm , ri
~ m
i
= − [δϕi Gi + δϕj Gj + δϕk Gk , ri ]
~
Two sides of the above would be consistent, if we require [Gi , rj ] = −i~ijk rk . Compar-
ing this relation with the commutator of the components of angular momentum L ~ with
position, viz., [Li , rj ] = i~ijk rk . Thus we identify G with −L and get
~ · L̂
δϕ
U = exp(i ) (14)
~
For rotation about z− axis, the rotation operator would be written as
δϕ · Lz
U (z, ϕ) = exp(i ) (15)
~
8
and similarly for the axis being along x− or y− directions.
If Uz commutes with the Hamiltonian, we may label the common eigenstate of H and Lz
with E and m. However, for rotationally invariant system (such as the hydrogen atom
problem) , they would not depend on m because Lx and Ly acting on a state of a given
m would give rise to states with m ± 1.

3 Discrete Transformations
3.1 Parity
We had seen that the rotational matrices satisfy RT R = I, which implies detR = ±1. The
subclass of matrices which satisfy detR = +1 are proper rotations which form a subgroup
SO(3) of the full rotation group O(3). The matrices with detR = −1 do not form a
subgroup because (i) it does not have the identity element and (ii) the product of two
elements of such a set has detR = +1 and hence does not form a subgroup. However, the
transformations of space inversions ~r = −~r form an important symmetry transformation
known as Parity. The same is true of momentum operator p~ which changes sign under
parity. These vectors (~r, p~ etc.) which reverse their sign under space inversion are known
as polar vectors or simply as vectors. In contrast, vectors such as angular momentum L ~
does not change sign under parity. They are known as pseudovectors or axial vectors.
Other example f a pseudovector is the magnetic field vector B. ~ One can look at the
expression for Biot Savart’s law to confirm that B ~ does not change sign when the space
coordinates are reversed. One can similarly distinguish between two classes of scalars,
viz. a scalar and a pseudoscalar. Under space inversion, a scalar does not change sign
whereas a pseudoscalar does. An example of a pseudoscalar is the magnetic flux which
being dot product of a pseudovector B ~ is a pseudoscalar.
~ and a polar vector dS
In quantum mechanics, we define a parity operator Π by its action on a state in the
position basis. Thus Π is a unitary operator, whose action on a state in the position bass
is given by
Π | ~ri =| −~ri (16)
This definition, along with its unitarity enables us to obtain some properties of the oper-
ator. Firstly Π2 = I. This is obvious because two application of Π would return the state
back to the original state ~r → −~r → +~r. It also follows from (16) that Π is hermitian.

9
To see this multiply both sides of the equation Π2 = I by Π† to get

Π2 P † = Π†
Π† ΠΠ = Π†

Using the unitarity, we have Π† Π = I which gives Π = Π† . The operator Π turns out
to be an observable (Experiment of Wu on beta decay of Cobalt by observing directional
property of emitted electrons and gamma rays when strong magnetic fields are applied
). Since Π2 = I, the eigenvalues of Π are ±1. Using the definition of a wavefunction
ψ(~r) = hψ | ~ri, we get the action of Π on the position space wavefunction as

Πψ(~r) = ψ(−~r)

ψ(~r) ± ψ(−~r)
The eigenstates of Π corresponding eigen values ±1 may be written as with
2
the plus sign corresponding to what is known as the even parity state, i.e., a state which
does not change sign under parity and the minus sign corresponds to the odd parity state,
which does change sign. For instance, the eigenfunctions of the orbital angular momentum
Ylm (θ, ϕ) has either odd parity or even parity depending on whether the quantum number
l is odd or even,

Ylm (θ, ϕ) → (−1)l Ylm (θ, ϕ)

Let’s look at what happens to the operators under parity? Consider position operator
first under which | ψi → r̂ | ψi. Since | ri is an eigenstate of the position operator with
eigenvalue r (and parallely, | −ri is of −r̂) we may write

hr | Πr̂ | ψi = h−r | r̂ | ψi
= −rh−r | ψi
= −rhr | Π | ψi
= −hr | r̂Π | ψi

Thus Π and r̂ anti-commute. A similar relation may be shown for the momentum operator.
Recall that the translation operator T̂ is given by
~a · p̂
T̂ (~a) = exp(−i )
~

10
The action of T̂ (~a) on the eigenstate of position is given by

T̂ (~a) | ~ai =| ~x + ~ai

Under the action of parity, the operator T̂ (~a) → Π† T̂ (~a)Π. Thus we have

Π† T̂ (~a)Π | ~xi = Π† T̂ (~a) | −~xi

= Π† | −~x + ~ai
= i~∇hr | Π | ψi
= Π† Π | ~x − ~ai
=| ~x − ~ai
= T̂ (−~a) | xi

which shows Π† T̂ (~a)Π = T̂ (−~a). Thus we have, taking infinite generator for translation
   
† i i
Π 1 − ~ · p̂ Π = 1 + ~ · p̂
~ ~

Expanding and keeping terms of order , it follows that Π† p̂Π = −p̂, i.e. p̂ and Π
anti-commute. However, as pointed out earlier, Π commutes with the orbital angular
momentum. To be consistent with the angular momentum commutation relations, we
take Π to commute with Jand ~ ~ Note that x̂ and Jˆ transform similarly under rotation
S.
though they have different behaviour under parity operation.
In general, for a vector operator V , we have ΠV Π† = −V whereas for a psedudovector
ΠÂΠ† = Â. A scalar is invariant both under rotation and parity whereas for a pseu-
doscalar, K we have ΠKΠ† = −K and U (R)KU (R)† = K.
Space inversion symmetry plays an important role in the selection rules of atomic tran-
sitions. Note that for long wavelength atomic transition, the transition rates are propor-
tional to the square of the matrix element of dipole operator ex̂ between initial and final
atomic states. Since the dipole operator has odd parity, this matrix element would be zero
unless the initial and the final atomic states have opposite parity. Recall that we pointed
out earlier that the atomic states have parity proportional to (−1)l . Thus the selection
rule for allowed transition is that the l value must change by ±1. This selection rule is in
addition to the rules imposed by Wigner-Eckart theorem discussed earlier. This implies

11
that no non-degenerate state has a dipole moment because hn | x | ni = 0. However, it
must be mentioned that parity is not conserved in weak interactions.
Examples
(1) Consider the Hamiltonian for one dimensional harmonic oscillator

p2 1
H= + mω 2 x2
2m 2
Recall the definition of ladder operators
r  
mω i
a= x̂ + p̂
2m~ mω
r  
† mω i
a = x̂ − p̂
2m~ mω

with the ground state being defined as a | 0i = 0. Since the Hamiltonian depends on
squares of x and p, it commutes wit the parity operator, [Π, H] = 0. Hence the energy
states of the oscillator have well defined parity. Note further that Πa† Π = −a† . This
gives
Π | n + 1i = πa† | ni = −a† Π | ni
If the eigenvalue of Π in the state | ni is denoted as πn , then

πn+1 | n + 1i = −a† πn | ni = −πn a† | ni = −πn | n + 1i

Thus πn+1 = −πn , which shows that the excited states of the harmonic oscillator alternate
in parity. Since the ground state is even, the parity of the n−th state is given by (−1)n .
(2) Consider hydrogen atom wavefunction. Since the potential energy term depends on
the distance | r | and the kinetic energy depends on p2 , the Hamiltonian is invariant under
parity transformation, meaning thereby the eigenfunctions of hydrogen atom have well
defined parity. This parity depends only on l value and is independent of m. To show this,
we consider the state of maximum m, i.e. m = l. For this case the spherical harmonic
takes a simple form
Yl,l = eilϕ sinl (θ)
Parity transformation implies θ → π − θ, ϕ → ϕ + π. Thus under parity, this state of
maximum l would become
eil(ϕ+π) sinl (π − θ)

12
Since sin(π − θ) = sin θ, and eilπ = (−1)l , we have

ΠYl,l = (−1)l Yl,l

Let us see what happens to the state with m = l − 1 under parity operation. Recall that
the state with m = l −1 is obtained from the state with m = l by application of the ladder
operator L− . Ignoring the multiplicative factor, we have | l, m = l − 1i = L− | l, m = li,
Thus

Π | l, m = l − 1i = ΠL− | l, li = L− Π | l, li = (−1)l L− | l, li = (−1)l | l, l − 1i

i.e., the state still has parity (−1)l . we may repeat the argument for lower values of l and
get the same result.

3.2 Time Reversal

Though the phrase “time reversal” is widely accepted in physics, a more appropriate
nomenclature would be to term this symmetry as reversal of motion. Time reversal itself
would violate the measurement principle as once the state has collapsed, it would not
be possible to precisely turn the sequence of the states which led to the present state.
However, the dynamics of the system when each component of the motion is reversed is
represented by letting t → −t in the equations.
Considering classical motion, Newton’s second law is invariant under t → −t because it
involves second derivative with respect to time. Hence of x(t) is a solution of the equation
x(−t) also is. However, if one includes a damping term in the equation of motion, the
system is not invariant under time reversal as the equation of motion now includes a
first derivative of position with respect to time. Situation is a little more complicated if
one considers electromagnetism. As the equations involves first derivative with respect
to time, it would appear that these equations are not time reversal invariant. However,
one has to take into consideration the fact that when the direction of velocity changes
sign, the direction of current also does so, (we assume that the charge remains invariant)
making the magnetic field B ~ also change sign. This would make, for instance, the term
∂B
remain invariant under time reversal. The electric field depends only on the charge
∂t
distribution and space coordinates and therefore remains invariant under time reversal.
With this prescription, Lorentz force becomes invariant under time reversal.
To see how the phrase “time reversal” becomes appropriate, consider the motion of a

13
particle under the action of a classical Hamiltonian H(~r, p~). Suppose at time t = 0, the
position and the momentum of the particle are given by ~r(0) and p~(0) respectively. Let
the position at time t be ~r(t) and momentum be p~(t). Starting from this instant, suppose
we wish to get back to the initial values of position and momentum after a time −t, as we
cannot change the direction of time at our will, what we do is to change the Hamiltonian
to a form H(~r, −~p) and run the process for a time t, we would then get back to the
original values of position and momentum after a time t in the forward direction. Thus
reversing the direction of momentum had the same effect as it would if we could reverse
the direction of time without having to change the Hamiltonian.
It would appear that all that needs to describe time reversal is to postulate an operator
Θ whose action on all time dependent quantities is to reverse their signs,
Θf (t) = f (−t)
However, this turns out to be unsatisfactory in quantum mechanics. To see this consider
what happens to the Schrödinger equation
∂
i~ ψ(~r, t) = Hψ(~r, t)
∂t
under time reversal. Since H has no explicit time dependence, when t → −t, the equation
would become
∂
−i~ ψ(~r, −t) = Hψ(~r, −t) (17)
∂t
which shows that ψ(~r, −t) is not a solution of the Schrödinger equation. For us to be able
to come to this result, we require that there exists an operator Θ which acting on the
state of the system gives the ”time reversed state”,
| ψi → Θ | ψi
As per our previous description, let us suppose we start from a state at time t = 0 denoted
by | ψ(0)i. Let this state develop for a time t driven by the Hamiltonian H so that at
time t the system is in the state | ψ(t)i, where
| ψ(t)i = e−iHt/~ | ψ(0)i (18)
Suppose we are to apply a time reversal operator Θ on | ψ(t)i and run the system exactly
for the duration of time t so that the state of the time reversed system becomes e−iHt/~ Θ |
ψ(t)i, we would then have arrived at the “time reversed state” Θ | ψ(0i,i.e.
e−iHt/~ Θ | ψ(t)i = Θ | ψ(0)i

14
because the time reversed state in the forward direction of time would retrace its original
path. If in this equation, we substitute (18) for | ψ(t)i, we would get

e−iHt/~ Θe−iHt/~ | ψ(0)i = Θ | ψ(0)i

As this equation must be true for all initial states | ψ(0)i, we get an operator relationship

e−iHt/~ Θe−iHt/~ = Θ (19)

which is equivalent to
e−iHt/~ Θ = Θe+iHt/~ (20)
For infinitesimal time t the above equation gives

−iHΘ = ΘiH

In normal situation, we could cancel the factor i from both sides getting −HΘ = ΘH.
Suppose | Ei is an eigenket of the Hamiltonian with energy E. We then would get

−HΘ | Ei = ΘH | Ei = EΘ | Ei

This implies that the state Θ | Ei is an eigenstate of the Hamiltonian with energy −E.
This, as we have seen in our comment in the last paragraph of the section on time trans-
lation operator (see comment following eqn. (12)), would make the ground state unstable
and is, therefore, an unacceptable situation. It even leads to an absurd situation in the
case of a free particle, suggesting that its time reversed state would have negative energy.
We therefore seek problem seek a resolution of the problem by looking for an alternative.
Recall that we had pointed out that the wavefunction itself is not observable. The prob-
ability, which is an observable, is preserved both by unitary operators and by operators
which we termed anti-unitary. If we assume that in this case our operators Θ is anti-
unitary, which has the following properties (see (4)):

Θ(c1 | αi + c2 | βi) = c∗1 Θ | αi + c∗2 Θ | βi

that is, the operator acts like a linear operator but complex conjugates the scalars which
multiply the states, it has no special action on the basis states themselves. Further, we
do not define action of Θ on a bra, i.e., the operator Θ only works on a ket to

15
its right.Thus, the operator Θ may be thought of as a product of a “complex conjugation
operator” K and a unitary operator U
Θ = UK (21)
where K operating on a scalar, complex conjugates everything to the right of it, giving,
for instance Ki = −iK and Kc | ψi = c∗ K | ψi. It has no effect on a real number.
Returning to the infinitesimal t version of (20), we would then get
[Θ, H] = 0
, which expresses the symmetry property of the Hamiltonian under time reversal. Re-
turning to (17), if we operate both sides of the equation by Θ = U K, remembering that
Θi = −iΘ, and the fact that Θ commutes with H, we get
∂
+i~ Θψ(−t) = HΘψ(−t)
∂t
Define
ψ̄(t) = Θψ(−t),
we get
∂
i~ ψ̄(t) = Hψ̄(t)
∂
which shows ψ̄(t) satisfies Schrödinger equation.
Let us now consider the transformation of the operators under time reversal. Define the
time reversed state corresponding to a state | αi by | α̃i = Θ | αi. Further, let us define
an operator à to be the time reversed operator corresponding to an operator  (we have
suppressed the hat(ˆ) sign on the time reversed form of the operator A to avoid clumsiness
of notation). By definition, we then have, for a hermitian observable Â,
hα̃ | Ã | β̃i = hα | Â | βi (22)
Let us define A† | αi =| γi, so that hγ |= hα | A. Thus, we have,
hα | A | βi = hγ | βi
= hβ̃ | γ̃i using anti − unitarity of the time − reversed states
= hβ̃ | Θ | γi
= hβ̃ | ΘA† | αi
= hβ̃ | ΘA† Θ−1 Θ | αi = hβ̃ | ΘA† Θ−1 | α̃i (23)

16
Note that in deriving the above, we have taken care so that Θ works only on the ket to
its right, never on a bra. If  is hermitian, we have, using A† = A

hα | A | βi = hβ̃ | ΘAΘ−1 | α̃i

An operator  is said to be even or odd under time reversal, if

ΘAΘ−1 = ±A

Taking α = β, it follows that the expectation value of an operator in the time reversed
state | α̃i is the same as in the state | αi if the operator A is even under time reversal
and is negative of the former if it is odd.

hα̃ |  | α̃i = hα | A | αi if  is even

= −hα | A | αi if  is odd

Coming to specific operators, we require expectation value of position operator x̂ to be

even and that of p̂ to be odd. Thus we have

hα | x̂ | αi = hα̃ | x̂ | α̃i

However, we have
hα | x̂ | αi = hα̃ | Θx̂Θ−1 | αi
Comparing the two expressions above, we get

Θx̂Θ−1 = x̂

In a similar way, we can show that since the expectation value of the momentum operator
changes sign under time reversal,
Θp̂Θ−1 = −p̂
It is easy to show that the commutation relation [xi , pj ] = i~δi,j becomes

Θ[xi , pj ]Θ−1 = −i~δi,j

~ −1 = −J.
We can also show that ΘJΘ ~

17
3.3 Charge Conjugation
Charge conjugation symmetry refers to invariance of physical laws when the particles are
replaced by their corresponding antiparticles. All charged particles have their antipar-
ticles, such as the positron corresponding to an electron, antiproton corresponding to a
proton etc. Some neutral particles such as γ and π 0 do not have antiparticles. However, it
is possible for a neutral particle to have an antiparticle. For instance the neutron has its
antiparticle, antineutron which is distinguished from neutron by having an opposite sign
for its magnetic moment. Antineutrino is distinguished from the neutrino by its having
an opposite helicity (component of spin in the direction of its motion).
We define charge conjugation operator C by its action on charge quantum number or on
its magnetic moment, i.e. it converts a particle to its antiparticle. Action of the charge
conjugation operator on the state of a particle with charge -parity state a is given by

Ĉψ(a) = Ca ψ(ã)

where ã is the charge- parity state of the antiparticle. Clearly, a further operation by Ĉ
would return it back to the original charge parity state. Hence, we have

Ca2 = 1 =⇒ Ca = ±1

Ca is called the charge parity. Charge parity is distinct from the charge of the particle. If
an interaction conserves C, then [H, C] = 0. Charge-parity is conserved in strong inter-
action but is violated in weak interaction. Let Q be the charge operator with eigenstate
| ψq i, i.e.
Q | ψq i = q | ψq i
We then have
CQ | ψq i = qC | ψq i = q | ψ−q i
However,
QC | ψq i = Q | ψ−q i = −q | ψ−q i
Thus [Q, C] 6= 0 unless q = 0. This shows that the charge operator is distinct from the
charge parity.
We will not discuss the charge conjugation in any more detail. It is covered in a particle
physics course more rigorously.

18
 Quantum Mechanics - II
Perturbation Theory- I
(Non-Degenerate Case)
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 29, 2019

1 Introduction
In Quantum Mechanics-I course, we have obtained exact solutions for problems such as
free particle, particle in a box, harmonic oscillator and hydrogen atom. We have obtained
solutions for the stationary states for these systems which are described by Hamiltonians
which do not have explicit time dependence. Unfortunately, problems for which exact
solutions can be obtained in quantum mechanics are very few. In most cases we have to
use approximate methods for solutions. There are three major approximation schemes:
perturbation theory, variational methods and WKB approximation. Our interest is pri-
marily in obtaining bound state energy and eigenstates.
In perturbation theory, we deal with systems whose Hamiltonians are slightly different
from systems which can be exactly solved. There are two distinct cases depending on
whether the solution of the solvable Hamiltonian has degenerate eigenvalues. We will
first consider the case where the exactly solvable problem has non-degenerate eigenval-
ues.. Examples of systems where we employ non-degenerate perturbation theory are free
particles in weak electric or magnetic field. The formalism is also known as Rayleigh-
Schrödinger perturbation theory.

2 Formal Expansion in a perturbation parameter

The system that we are interested in is described by a Hamiltonian H which can be
written as a sum of an unperturbed, exactly solvable part H and a perturbation V :

H = H0 + V (1)
where the eigenvalues and eigenstates of the unperturbed Hamiltonian are given, respec-
tively by En0 and | ψn0 i,
H0 | ψn0 i = En(0) | ψn0 i (2)
(H0 + V ) | ψn i = En | ψn i (3)
To make the smallness of the perturbation explicit, we take the interaction term of the
Hamiltonian to be λV , where λ is a continuous parameter. At the end of the calculation,
we take the limit λ → 1. For cases where perturbation works, we usually have λ  1.
The basis of the method rests on expansion of eigenvalues and eigenfunctions in powers
of λ. This does not always work because even when λ is small, there may not be an
expansion of eigenvalues and eigenvectors in a small parameter, i.e., the function may not
be analytic about λ = 0 in the complex λ plane. Further, the series expansion may not
converge. However, in many cases of interest, it suffices to keep one or two terms in the
expansion without worrying about the convergence series.
0
We assume that {| ψm i} to be complete and also that the energy spectrum of the unper-
turbed Hamiltonian to be non-degenerate. Let
En = En(0 + λEn(1) + λ2 En(2) + . . . (4)
| ψn i =| ψn0 i + λ | ψn1 i + λ2 | ψn2 i + . . . (5)
(k)
which gives the correct limit for λ = 0. | ψnk i and En correspond, respectively, to the
k−th order correction to the n−th eigenstate and the eigenvalue of the Hamiltonian. We
will be interested in the first two orders of correction.
Using (3), we can write the Schrd̈inger equation as
(H0 +λV )[| ψn0 i+λ | ψn1 i+λ2 | ψn2 i+· · · ] = (En(0) +λEn(1) +λ2 En(2) +· · · )[| ψn0 i+λ | ψn1 i+λ2 | ψn2 i+· · · ]
(6)
Equation (6) must be valid for all (small) values of λ, thus enabling us to equate the
coefficients of equal powers of λ on both sides. This gives us an infinite system of equations
(En0 − H0 ) | ψn0 i = 0 (7a)
(En0 − H0 ) | ψn1 i + En1 | ψn0 i =V | ψn0 i (7b)
(En0 − H0 ) | ψn2 i + En1 | ψn1 i + En2 | ψn0 i =V | ψn1 i (7c)
... = ...
(En0 − H0 ) | ψnm i + En1 | ψnm−1 i + Enm | ψn0 i = V | ψnm−1 i (7d)
Equation (7a) is just a statement of the fact the | ψn0 i is an eigenket of the unperturbed
Hamiltonian H0 with eigenvalue En0 . The remaining equations relate the energy and state
in a given order with those of the previous orders. Note that the equation (7d) for the
arbitrary m−th order remains unchanged if we add to | ψnm i, a constant multiple of | ψn0 i
because of (7a). Thus we are free to choose this constant multiple in such a way that the
correction | ψnm i in any order is orthogonal to the zeroth order eigenket | ψn0 i, so that
hψn0 | ψnm i = 0
for every m 6= 0.
We will explain this point more explicitly in our discussion of the first order pertur-
bation theory.
If we take the scalar product of the equation (7d) with hψn0 |, and use the fact that
H is Hermitian and also the fact that the energy levels are non-degenerate, we have
hψn0 | H0 = hψn0 | En0 , we get, in view of the orthogonality discussed above,

Enm = hψn0 | V | ψnm−1 i (8)

where we have assumed that the wavefunctions are appropriately normalized. Thus cal-
culation of the perturbed energy to any order m requires a knowledge of the eigenstate
of the Hamiltonian H to the next lower order m − 1.

2.1 First Order Perturbation

Retaining terms to order λ, we get, on using (7b),

H0 | ψn1 i + V | ψn0 i = En(0) | ψn1 i + En(1) | ψn0 i (9)

0
Since {| ψm i} is a complete set of states, we can expand | ψn1 i
X
| ψn1 i = 0
an,m | ψm i (10)
m

Using (10) we can write this equation as

X X
0
H0 an,m | ψm i + V | ψn0 i = En(0) 0
an,m | ψm i + En(1) | ψn0 i (11)
m m

0
Since | ψm i are eigenkets of H0 , we can rewrite this equation as
X X
(0) 0
an,m Em | ψm i + V | ψn0 i = En(0) 0
an,m | ψm i + En(1) | ψn0 i (12)
m m

Taking a scalar product with hψl0 | and using orthogonality of the unperturbed basis set,
we get,
(0)
El an,l + hψl0 | V | ψn0 i = En(0) an,l + En(1) δn,l (13)
From (13), we get, on taking l = n,

En(0) an,n + hψn0 | V | ψn0 i = En(0) an,n + En(1) (14)

which gives the first order correction to the n− th energy level

En(1) = hψn0 | V | ψn0 i (15)

which agrees with the general expression (8) derived earlier. We now need to determine
the correction to the state of the system in this order. From (13), we get for l 6= n,
(0)
(En(0) − El )an,l = hψl0 | V | ψn0 i (16)

from which we get,

hψl0 | V | ψn0 i
an,l =
(0) (0)
(17)
(En − El )
Thus we have an expression for all an,l except an,n . We can get information about this
as well by imposing the condition that the perturbed state | ψn i =| ψn0 i + λ | ψn1 i is
(2)
normalised. As we have not included | ψn2 i and En in our calculation, the normalisation
equation also needs to be calculated to order λ as well. We have,

hψn0 + λψn1 | ψn0 + λψn1 i = 1

Taking λ to be a real parameter, this gives

hψn0 | ψn0 i + λhψn1 | ψn0 i + hψn0 | ψn1 i = 1

Since the unperturbed states are normalised, the first term on the left is 1 and we get, on
using (10) for the first order change in the state | ψn1 i,
X X
λ[ a∗n,m hψm
0
| ψn0 i + an,m hψn0 | ψm
0
i] = 0
m m
0
Using hψm | ψn0 i = δm,n , this gives

a∗n,n + an,n = 0

which implies that the coefficient an,n is purely imaginary. Denoting this by iφ, we have,

| ψn i =| ψn0 i + λ | ψn1 i
X
=| ψn0 i + λ 0
an,m | ψm i
m
X
=| ψn0 i(1 + λan,n ) + λ 0
an,m | ψm i
m6=n
X
=| ψn0 i(1 + iλφ) + λ 0
an,m | ψm i (18)
m6=n

Since λ is small, we can write 1 + iλφ = eiλφ and (18) can be written as,
X
| ψn i =| ψn0 ieiλφ + λ 0
an,m | ψm i (19)
m6=n

Now the factor eiλφ is a phase factor which can be absorbed in | ψn0 i itself as an overall
phase in the unperturbed state is of no significance at all. Thus we have,
X
| ψn i =| ψn0 i + λ an,m | ψm0
i (20)
m6=n
which can be write, using (17) and on setting λ = 1,

X hψ 0 | V | ψ 0 i
m n
| ψn i =| ψn0 i + (0) (0)
0
| ψm i (21)
m6=n (En − Em )

This is the corrected state in the first order.

2.2 Second Order Perturbation

Returning to (6), if we equate terms proportional to λ2 , we get

H0 | ψn2 i + V | ψn1 i = En(0) | ψn2 i + En(1) | ψn1 i + En(2) | ψn0 i (22)

0
As before, multiply both sides of above by the eigenbra hψm | of H0 ,
(0) 0
Em hψm | ψn2 i + hψm
0
| V | ψn1 i = En(0) hψm
0
| ψn2 i + En(1) hψm
0
| ψn1 i + En(2) hψm
0
| ψn0 i
(0) (0) (0)
Taking m = n and using the Taking m = n and using the fact that hψn | ψn i = 1; hψn |
(1) (0) (2)
ψn = hψn | ψn ii ' 0, we get

En(2) = hψn(0) | V | ψn(1) i (23)

(1)
Substituting the expression (9) for | ψn i in the above, we get,
(0) (0)
X | hψm | V | ψn i |2
En(2) = (0) (0)
(24)
m6=n En − Em

Note that :

1. energy in the k-th order is determined by the state vector in the (k-1)-th order.

2. Perturbation expansion is good if the corrections are small ; i.e.

(0) (0)
hψm | V | ψn i
| (0) (0)
|1
En − Em
(0) (0)
If En = Em , i.e. if the unperturbed states are degenerate, theory breaks down
and one must use degenerate perturbation theory.

3 Examples
Example 1 : Consider particle in a box centered at x = 0 with walls at ±a. A perturbing
potential V (x) = aV0 δ(x) acts on the system. Determine the first and the second order
energy change for the odd and the even parity solutions. What is he perturbed state in
the first order of perturbation theory?
Solution:
With the boundary condition ψ(x = ±a) = 0, the even and the odd parity solutions are
1
ψodd (x) = √ sin(2nπx/2a)
a
1 (2n − 1)π
ψeven (x) = √ cos( x)
a 2a

~2 π 2 n2
with En0 = .
8ma2
In the first order perturbation theory

∆En1 = hψn | aV0 δ(x) | ψn i = aV0 ψn (0)2

which gives
1
∆En,odd =0
1
∆En,even = V0

In the above, odd and even refer to the solution type and not to the values of n which
can be 1, 2, 3, . . ..
To determine the change in the wavefunction in this order we need to calculate hψm |
aV0 δ(x) | ψn i for m 6= n.
For the odd solutions, we have ψm (0)aV0 ψn (0) = 0 because ψn (x) is a sine function which
vanishes at x = 0 irrespective of what the value of ψm (0) might be. Thus for the odd
solutions, the wavefunction, like the energy does not change in the first order.
For the even solutions, ψn (x) is a cosine function which does not become zero at x = 0.
However for the case where ψm is odd, the integral would still vanish because ψm (0) = 0
for odd solutions. Thus the matrix elements would not vanish only if both ψn and ψm
refer to even solutions, in which case
X aV0
∆En (x) = ψ (x)
0 m
E0
m6=n,ψm even n
− Em

For the second order energy change, we need to calculate |hψm | aV0 δ(x) | ψn i|2 for m 6= n.
As before this is non-zero when both ψm and ψn belong to the even solutions. We then
have
X a2 V02 X V02
∆En(2) = ψ
0 m
2
(0)ψn
2
(0) =
E 0 − Em
m6=n,ψ even n
E 0 − Em
m6=n,ψ even n
0
m m

The sum above can be done and it gives the second order energy change to be

V02
∆En = −
4E0 n2
where n is odd (the solutions for which are even).

Example 2: Linear harmonic oscillator in an electric field

Consider a particle with charge q subject to an external electric field E. Show that the
second order perturbation for energy gives the exact energy for the problem. Show further
that the change in the wavefunction in first order gives the exact wavefunction for the
problem.

Solution: The Hamiltonian for the problem is

p2 1
H = H0 + V = + mω 2 x2 − qEx (25)
2m 2
The Hamiltonian above may be expressed as
2
p2 q2E 2

1 2 qE
H= + mω x − −
2m 2 mω 2 2mω 2

One can see that the above Hamiltonian represents a liner harmonic oscillator whose
qE q2E 2
origin has been shifted to x = and the energy shifted by . We will now use
mω 2 2mω 2
perturbation theory to the Hamiltonian (25). Recalling that the ladder operators are
given by
r
~
x= (a + a† )
r2mω
m~ω †
p=i (a − a)
2
we get the first order correction to be zero as
r
~
∆En1 = hn | −qEx | ni = qE hn | a + a† | ni = 0
2mω
In order to calculate the second order energy change, we need to calculate the matrix
element hm | V | ni, and we get
r
~
hm | V | ni = −qE hm | a + a† | ni
r 2mω
~ h√ √ i
= −qE nhm | n − 1i + n + 1hm | n + 1i
r 2mω h
~ √ √ i
= −qE nδm,n−1 + n + 1δm,n+1
2mω
Thus, for the second order energy change we get
 
(2) 2 2 ~ n n+1
∆En = q E +
2mω En − En−1 En − En+1
 
2 2 ~ n n+1
=q E +
2mω ~ω −~ω
2 2
q E
=−
2mω 2
which is the exact solution obtained above.
Let us return to the change in the state of the system in the first order of perturbation
theory, which is given by (21) to be

X hm | V | ni
∆ | ψi = | mi
E n − Em
m6=n
r √ √ 
~ n n+1
= −qE | n − 1i + | n + 1i
2mω ~ω −~ω
r
~ 1 
a | ni − a† | ni

= −qE
r 2mω ~ω
~ 1
= −qE (a − a† ) | ni
2mω ~ω
iqE
=− p̂ | ni
mω 2 ~
where we have used the expression for the momentum operator in terms of the ladder
operators. To see that the result agrees with the first order change obtained above, note
qE
that the the origin of the harmonic oscillator states are shifted by so that, the change
mω 2
in the wavefunction is given by performing a Taylor expansion
qE qE d iqE
ψ(x − ) = ψ(x) + ψ(x) = − p̂ψ(x)
mω 2 mω 2 dx mω 2 ~
Example 3:
Consider an infinite potential well from 0 to x = a with a small rectangular bump of
height δV0 lying between a/3 ≤ x ≤ 2a/3. Calculate the change in the energy in the first
order of perturbation theory.
 V (x)
∞

δV0
0 x
a/3 2a/3 a

Solution:
Since the infinite well is from x = 0 to x = a, the unperturbed wavefunctions are
r
2
sin(nπx/a)
a
for 0 ≤ x ≤ a and is zero outside this range. Thus the energy change in the first order is
Z 2a/3 " √ #
2 1 3
∆En(1) = δV0 sin2 (nπx/a)dx = δV0 +
a a/3 3 2π

Thus the shift in energy is positive if δV0 is positive and is negative if δV0 is negative.
To determine change in the wavefunction, we need to compute hm | δV0 | ni for m 6= n.
Since δV0 is constant we need to evaluate the integral
Z 2a/3
sin(mπx/a) sin(nπx/a)dx
a/3

for m 6= n. The integral is easily computed by expressing the product of the sine functions
as difference of sum and difference of cosines. The correction to the wavefunction is found
to be √ r
3 3ma2 2
' δV0 sin(3πx/a)
16π 3 ~2 a
4 Applications
4.1 Stark Effect in the Ground State of Hydrogen Atom
If an hydrogen atom is placed in a weak, uniform electric field along the z - direction, the
Hamiltonian of the system is given by
p2 e2
H= − − eEz
2µ r
The eigenfunctions of the unperturbed Hamiltonian are known to be given by
ψnl (r, θ, φ) = Rnl (r)Ylm (θ, φ)
We can apply non-degenerate perturbation theory only to the ground state of the hydrogen
atom as all the excited states are degenerate. In the first order of perturbation, the change
in the energy is Z
h100 | (−eEz) | 100i = | ψ100 |2 zd3 r = 0

because the ground state wavefunction has definite parity, so that the integrand is odd in
z. There is, thus, no linear stark effect. The physical origin of this is the fact that there
is no permanent dipole moment in the ground state. The second order effect is, however,
not zero and is given by
X | hnlm | z | 100i |2
∆E = e2 E 2 (0) (0)
(26)
n,l,m6=100 E 100 − Enlm

∆E is negative because the denominator of each term in the sum is negative. While
the sum on the right hand side cannot be exactly performed, we can get an estimate
of the change in the ground state energy by replacing the denominator of eqn. (11) by
(0) (0)
E100 − E200 as
(0) (0) (0) (0) e2 e2 3e2
| E100 − Enlm |≥| E100 − E200 |=| − + |=
2a0 8a0 8a0
Thus
8a0 X
| ∆E | ≤ e2 E 2 | hnlm | z | 100i |2
3e2 nlm6=100
2
8a0 E X
= h100 | z | nlmihnlm | z | 100i
3 nlm6=100
2
8a0 E X (27)
= h100 | z | nlmihnlm | z | 100i
3 nlm
8a0 E 2 X
= h100 | z | nlmihnlm | z | 100i
3 nlm
8a0 E 2
= h100 | z 2 | 100i
3
In eqn. (12) in arriving from the step (2) to the step (3) we have used the fact that
h100 | z | 100i = 0 so that the restriction on the summation is removed. In arriving at
the final step we have used the completeness relation of the set of unperturbed states, viz.
P
nlm | nlmihnlm |= 1.
Thus we need to calculate the matrix element of z 2 in the ground state of the hydrogen
atom. The ground state wavefunction is known to be given by

ψ100 = R10 (r)Y00 (θ, φ)

1 2 −r/a0
=√ e
4π a03/2
The matrix element is given by (using spherical polar and z = r cos θ)
Z
1 4
2
h100 | z | 100i = 3
e−2r/a0 (r2 cos2 θ)d3 r
4π a0
Z ∞ Z π
1 4 −2r/a0 4
= 3
(2π) e r dr cos2 θ sin θdθ
4π a0 0 0
2 ∞ −2r/a0 4
Z Z π
= 3 e r dr cos2 θ sin θdθ
a0 0 0
5
2 3a 2
= 3 0
a0 4 3
= a20
Hence
8
| ∆E |≤ a30 E 2
3

4.2 Charged particle in a harmonic oscillator potential and an

electric field
The Hamiltonian for the system is given by
~2 d2 1
H=− 2
+ mω 2 x2 − qE x̂ (28)
2m dx 2
This Hamiltonian is exactly solvable by completion of square but it provides a good
situation to test perturbation theory. The exact solution is as follows. The Hamiltonian
(28) can be written as
2
~ 2 d2 1 q2E 2

1 2 qE
H=− + mω x − −
2m dx2 2 mω 2 2 mω 2
~2 d2 1 2 2 1 q2E 2
=− + mω y −
2m dy 2 2 2 mω 2
where  
qE
y = x−
mω 2
This is just a linear harmonic oscillator problem with the origin of energy shifted. The
solutions are Hermite polynomials with energies being given by

1 q2E 2
 
1
En = n + ~ω −
2 2 mω 2

with n = 0, 1, 2, . . .. Let us look at the problem in a different way. We can treat the
electric field term as a perturbation on the harmonic oscillator problem described by the
first two terms of (28). The unperturbed energies are then given by (n + 1/2)~ω. Let
us represent the states in the occupation number representation corresponding to this
energy by | n(0) i. The perturbation operator V can be written by using the number
representation of the position operator x̂ as
r
~
V = −qE x̂ = −qE (a + a† ) (29)
2mω
The first order perturbation theory gives ∆E = 0 since hn | x̂ | ni = 0. This is a
consequence of the fact that in the coordinate representation, the states are Hermite
polynomials which have definite parity. The second order correction, however, does not
vanish. Let us look at the states in the first order as they decide the energy shift in the
second order. Using eqn. (9), the states in the first order can be written in the number
representation as
X 0 hm | V | ni0
| ni1 =| ni0 + (0) (0)
| mi0
m6=n En − Em

where the subscript 0 indicates states of the unperturbed Hamiltonian and the superscript
1 indicates the states of the full Hamiltonian in the first order of perturbation. Since V
contains a + a† , the terms in the summation can only be nonzero for m = n ± 1. Using
(29) for V , it is easy to see that
r
~ √ √ 
V | ni0 = qE n | n − 1i0 + n + 1 | n + 1i0
2mω
Thus
r √ √ 
~ n 0 hm | n − 1i0 + n + 1 0 hm | n + 1i0
| ni1 =| ni0 + qE (0) (0)
2mω En − Em
r "√ √ #
~ n | n − 1i0 n + 1 | n + 1i0
=| ni0 + qE + (30)
2mω En(0) − En−1(0) (0)
En − En+1
(0)
r
~ 1 √ √ 
=| ni0 + qE n | n − 1i0 − n + 1 | n + 1i0
2mω ~ω
 (2)
Using (23) we have, En = 0 hn | V | ni1 . It can be seen that
r
~
V | ni1 = −qE (a + a† ) | ni1
2mω "
r r
~ √ ~ qE √ √ √ √ 
= −qE n | n − 1i0 − n n − 1 | n − 2i0 − n + 1 n + 1 | ni0
2mω 2mω ~ω
r #
√ ~ qE √ √ √ √ 
+ n + 1 | n + 1i0 − n n | ni0 − n + 1 n + 2 | n + 2i0
2mω ~ω

The second order correction to energy is obtained by multiplying both sides with 0 hn |

q2E 2
En(2) = − (31)
2mω 2
It can be seen that this is the change in energy obtained by exact solution of the problem.

4.3 Ground state energy of Helium atom

Helium atom has Z = 2 and two electrons. Neglecting the interaction between the
electrons, the problem is one of two independent hydrogen-like atoms. The ground state
energy of each electron is −1.Z 2 = −4 Ryd. Thus the ground state energy of the Helium
atom, neglecting the electron-electron interaction should be −8 Ryd. The ground state
wavefunction is then a product of two atomic wavefunctions ψ(r1 , r2 ) = ψ(r1 )ψ(r2 ), where
1/2
Z3

ψ(r1 ) = ψ100 = e−Zr1 /a0
πa30

We will estimate the correction due to inclusion the Coulomb interaction e2 / | r1 − r2 |

between the two electrons in the first order of the perturbation theory. (In this derivation
we will keep the factor Z till the end of the calculation as we need to use this in the
application of the variational principle to the Helium atom later in the course)

| ψ(r1 , r2 ) |2 3 3
Z
2
∆E = e d r1 d r2
| r1 − r2 |
 
2Zr1 2Zr2
 3 2 Z exp − −
2 Z a0 a0
=e 3
d3 r1 d3 r2
πa0 | r1 − r2 |

It is convenient to use dimensionless variables by letting

r1 r2
→ r1 ; → r2
a0 a0
so that
d3 r1 d3 r2 → (a0 )6 d3 r1 d3 r2 and | r1 − r2 |→ a0 | r1 − r2 |
This gives

2Z 6 exp (−2Zr1 − 2Zr2 ) 3 3 2Z 6

Z Z
∆E = 2 E0 d r1 d r2 = 2 E0 I(r2 )d3 r2 (32)
π | r1 − r2 | π

e2
where E0 = = 1 Ryd. and we have defined
2a0
Z
exp(−2Zr1 ) 3
I(r2 ) = d r1
| r1 − r2 |

and θ to be the angle between ~r1 and ~r2 ,

Z
exp(−2Zr1 )
I(r2 ) = p d3 r1
r1 + r22 − 2r1 r2 cos θ
2
Z ∞ Z π
2 exp(−2Zr1 )
= 2π r1 dr1 p sin θdθ
0 0 r12 + r22 − 2r1 r2 cos θ

The angle integral can be done as follows : Let cos θ = µ. The angle integral becomes
Z 1
dµ 2  2 2 1/2 1

2 2 1/2
= (r1 + r 2 − 2r1 r2 µ) −1
−1 (r1 + r2 − 2r1 r2 µ) −2r1 r2
1
=− [| r1 − r2 | −(r1 + r2 )]
r1 r2
2


 if r1 > r2
= r21

 if r1 < r2
r2
Substituting the above in the expression for I(r2 ), we have
 Z r2 Z ∞ 
1 2 −2Zr1 −2Zr1
I(r2 ) = 4π r e dr1 + r1 e dr1
r2 0 1 r2

The following indefinite integrals can be used to evaluate the above

e−αr
Z
re−αr dr = − 2 (1 + αr) (33)
α
e−αr
Z
r2 e−αr = − 3 (2 + 2αr + α2 r2 ) (34)
α
Using these, we get

e−2Zr2 e−2Zr2
   
1 1 2 2
I(r2 ) = 4π − (2 + 4Zr2 + 4Z r2 ) + (1 + 2Zr2 )
r2 4Z 3 (2Z)3 4Z 2
π 
1 − e−2Zr2 − Zr2 e−2Zr2

= 3
Z r2
 Using (32) the energy can be written as

2Z 3 E0
Z
1 
e−2Zr2 1 − e−2Zr2 − 2r2 e−2Zr2 d3 r2

∆E =
π r2
3 Z ∞
2Z E0
e−2Zr2 1 − e−2Zr2 − 2r2 e−2Zr2 r2 dr2
 
= 4π
π 0

From (33) it follows that

Z ∞
1
e−αr dr =
0 α
Z ∞
1
re−αr dr = 2
0 α
Z ∞
2
r2 e−αr = 3
0 α
The energy, therefore, is given by
1 1 1 5Z
∆E = 8Z 3 E0 ( 2
− 2
−2 2
)= E0 (35)
4Z 16Z 64Z 4
Adding this to the energy obtained by neglecting electron-electron interaction, we get the
energy of the ground state of Helium atom to be −8 + 2.5 = −5.5 Rydbergs = −74.8 eV,
which is reasonably close to the experimentally obtained value of −78.98 eV. We will be
able to refine this result even further when we discuss the variational principles.
 Quantum Mechanics - II
Approximation Methods :
Perturbation Theory - II
(Degenerate Case)
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 29, 2019

1 Introduction
(0)
In the non-degenerate perturbation theory, we had a unique state | ψn i corresponding to
(0)
energy En to which the perturbed system approached at the parameter λ → 0. however,
if the zeroth order eigenstate is degenerate, it means that in addition to the energy, there
is some other observable, say A, which characterizes the states. Our basis states are then
eigenstates of both H0 and the operator Â
(0) (0) (0)
H0 | ψmα i = Em | ψmα i
(0)
where α is a quantum number corresponding to Â. The energy Em is independent of
(0)
the index α. This implies that any linear combination of | ψmα i with α = 1, 2, . . . is an
eigenstate of H0 . Thus, if we start from any unperturbed state and doing a perturbation
expansion reach a perturbed state and then reduce the parameter λ to approach zero, we
may arrive at a totally different linear combination of the basis states. If [V, A] 6= 0, the
zeroth order eigenstates of H = H0 + V are not eigenstates of Â. This lifts the degeneracy
associated with H0 .
For simplicity, let us take the unperturbed state to be two-fold degenerate. Let

H | ψn i = (H0 + V ) | ψn i = En | ψn i (1)

The unperturbed energy levels are given by

(0)
H0 | ψnα i = En(0) | ψnα
(0)
i, where α = 1, 2 (2)
 (0)
The states {| ψnα i} are orthonormalized
(0) (0)
hψnα | ψnβ i = δα,β

In the lowest order of approximation, we can write

(0) (0)
| ψn i = a01 | ψn1 i + a02 | ψn2 i

where a01 and a02 are constants. Substituting this in (1) we have
   
(0) (0) (0) (0)
(H0 + V ) a01 | ψn1 i + a02 | ψn2 i = En a01 | ψn1 i + a02 | ψn2 i
     
(0) 0 (0) 0 (0) 0 (0) 0 (0) 0 (0) 0 (0)
En a1 | ψn1 i + a2 | ψn2 i + V a1 | ψn1 i + a2 | ψn2 i = En a1 | ψn1 i + a2 | ψn2 i
(3)
(0) (0)
From (3), multiplying both sides by hψn1 | and hψn2 |, we get the following equations for
the coefficients a01 and a02 .
(0) (0) (0) (0)
En(0) a01 + a01 hψn1 | V | ψn1 i + a02 hψn1 | V | ψn2 i = En a01 (4)
(0) (0) (0) (0)
En(0) a02 + a01 hψn2 |V | ψn1 i + a02 hψn2 |V | ψn2 i = En a02 (5)

These are simultaneous equations in the coefficients a01 and a02 and the solutions exist only
if the secular determinant vanishes, i.e.,
(1)
V11 − En V12
(1) =0 (6)
V21 V22 − En

(0) (0) (1) (0)

where, Vαβ = hψnα | V | ψnβ i and En = En − En . The solution of (6) gives the change
in energy in the first order perturbation,
p
En(1) = −(V11 − V22 ) ± (V11 − V22 )2 + 4V12 V21 (7)

The eigen vectors which removes the degeneracy are the eigen vectors that diagonalize
the matrix. These are the states to which the perturbed state approaches in the limit of
λ → 0. The above can easily be extended to the case where the degeneracy is g-fold. In
this case the secular equation is an g × g matrix.

2 Examples
2.1 Linear Stark Effect in Hydrogen Atom
We have seen that because of degeneracy of levels for n > 1, it was not possible to use
the non-degenerate perturbation theory for the excited states of hydrogen atom. Let us
consider n = 2 level of the H-atom. The energy of the state is −1/4 Ry and the state
is 4-fold degenerate (we ignore the spin degeneracy here which cannot be lifted by the
electric field). The perturbation Hamiltonian is
V = −ez | E |= −er cos θ | E |
The unperturbed states have the singlet state l = 0 and the triplet state l = 1 with m =
−1, 0, +1. We need to construct the secular matrix with element hl, m | V | l0 , m0 i. Since
V depends only r and θ and is independent of the azimuthal angle φ, hl, m | V | l0 , m0 i = 0,
except when m = m0 . Further, Since V is of odd parity, it can only connect states of
opposite parity, i.e. it gives non-zero value only between states of l = 0 and l = 1. In this
case the only non vanishing state is h0, 0 | V | 1, 0i and its conjugate. The matrix element
can be calculated using explicit forms of the hydrogen atom wavefunctions ψn,l,m , which
for n = 2, m = 0 are
 
1 1 r
ψ2,0,0 = √ p 3 1 − e−r/2a0
4π 2a0 2a0
r
3 1 r −r/2a0
ψ2,1,0 = p e cos θ
4π 6a30 2a0
The matrix elements are calculated in position representation as follows :
√ Z ∞  Z π
3 1 1 r 4 −r/a0
h2, 0, 0 | r cos θ | 2, 1, 0i = √ 3 2π 1− r e cos2 θ sin θdθ
4π 12a0 2a0 0 2a0 0
Z ∞  Z 1
1 r
= 4
1− r4 e−r/a0 µ2 dµ (where µ = cos θ)
8A0 0 2a0 −1
 
1 2·3·4 1 2·3·4·5
= −
12a40 (1/a0 )5 2a0 (1/a0 )6
a0
= (24 − 60) = −3a0 (8)
12
Using (8) in the 4 × 4 secular equation, we have
| 2, 0, 0i | 2, 1, 0i | 2, 1, 1i | 2, 1, 1̄i
| 2, 0, 0i 0 −3a0 0 0
−eE | 2, 1, 0i −3a0 0 0 0 =0 (9)
| 2, 1, 1i 0 0 0 0
| 2, 1, 1̄i 0 0 0 0
If one looks at the left hand corner of the matrix, it can be seen to be proportional to
Pauli’s σx with eigenvalues ±1. Thus the eigenvalues of the secular equation are
∆E = ±3eEa0 (10)
The corresponding eigen vectors can be readily found to be
1
ψ+ = √ (| 2, 0, 0i+ | 2, 1, 0i) (11)
2
1
ψ− = √ (| 2, 0, 0i− | 2, 1, 0i) (12)
2
Note that the states | 2, 1, 1i and | 2, 1, 1̄i are still degenerate with the unperturbed eigen-
value −1/4 Ry.
Comments :

• The 2s and 2p levels shown in the figure are really degenerate. Due to the spin-orbit
interaction, the 2p level splits into 2p1/2 and 2p3/2 . There is, however, degeneracy
persisting between 2s1/2 and 2p1/2 levels.

• The degeneracy between 2s1/2 and 2p1/2 levels is removed in QED due to Lamb shift.
However, the energy separation introduced by the degenerate perturbation theory
is much larger than the Lamb shift.

1
√ (| 2, 0, 0i− | 2, 1, 0i)
2

| 2, 1, 1i and | 2, 1, 1̄i
four fold

1
√ (| 2, 0, 0i+ | 2, 1, 0i)
2

Figure 1: Stark Effect splitting in Hydrogen Atom

2.2 Two dimensional Harmonic Oscillator with perturbation

Consider a two dimensional oscillator with the Hamiltonian
~2 d2 d2 1
H0 = − ( 2 + 2 ) + mω 2 (x2 + y 2 ) (13)
2m dx dy 2
The energies of the oscillator are given by
1 1
(nx + )~ω + (ny + )~ω
2 2
The first excited level has a two fold degeneracy (nx = 0, ny = 1 and nx = 1, ny = 0)
with an energy of 2~ω. In occupation number representation the states of the system are
denoted by | 0, 1i and | 1, 0i where the first index refers to the x-oscillator and the second
to y-oscillator. Now, a perturbation V = mλω 2 x̂ŷ is applied to the system. The resulting
secular equation can be easily obtained by going over to the representation for x and y
r
~
x̂ = (a + a† )
r 2mω
~
ŷ = (b + b† )
2mω
The perturbation is then given by
~ω
λ (a + a† )(b + b†
2
The non-zero matrix elements of the perturbation are as follows :
~ω
V12 = λ h0, 1 | (a + a† )(b + b† ) | 1, 0i
2
The operator a, a† acts only on the first index while the operators b, b† only on the second.
This gives
~ω
V12 = λ
2
A similar calculation gives V21 = V12 . Thus the energy shifts are given by

~ω
−E (1) λ
2 =0
~ω
λ −E (1)
2
~ω
which gives the energy shifts to be ±λ . The eigen states of the perturbed Hamiltonian
2
| 01i± | 10i
can be seen to be .
2
Let us consider the next excited states which are three fold degenerate. These states
are | 2, 0i, | 1, 1i and | 0, 2i. The unperturbed energy is 3~ω. Let the ladder operators for
the motion in the x and y directions be noted by a(a† ) and b(b† ). We then have

~
V = kxy = k (a + a† )(b + b† )
2mω
where the operators a’s commute with the operator b’s. We need the matrix elements
~
hmx , my | V | nx , ny i = k hmx , my | (a + a† )(b + b† ) | nx , ny i. Since a, b, a† , b† either
2mω
create or destroy, the diagonal matrix elements are all zero. The only non-zero elements
are

h1, 1 | V | 2, 0i, h1, 1 | V | 0, 2i, h2, 0 | V | 1, 1iand h0, 2 | V | 1, 1i

 k~
and each of these matrix elements is equal to √ ≡ δ. The matrix V is then
2mω
 
| 2, 0i | 1, 1i | 0, 2i
| 2, 0i 0 δ 0 
 
V =
| 1, 1i δ 0 δ 

| 0, 2i 0 δ 0

The secular determinant is

E −δ 0
−δ E −δ = 0
0 −δ E
√
which has the solution E = 0, ± 2δ. The corresponding eigenstates may be easily found
1 1 √ 1 √
to be √ (| 2, 0i− | 0, 2i), (| 2, 0i + 2 | 1, 1i+ | 2, 0i) and (| 2, 0i − 2 | 1, 1i+ | 2, 0i).
2 2 2
 Quantum Mechanics - II
Approximation Methods :
Perturbation Theory -III
(Fine Structure of Hydrogen Atom)
Dipan Kumar Ghosh
Physics Department, Indian Institute of Technology Bombay
Powai, Mumbai 400076
February 12, 2014

1 Introduction
There are two corrections to the energy levels of hydrogen atom calculated by non-
relativistic quantum mechanics. These lead to small corrections in the energy values
and give rise to what is known as the fine structure of hydrogen atom.

1.1 Relativistic correction

In relativistic theory, the kinetic energy of the electron is given by
p
T = m2 c4 + p2 c2 − mc2

where m is the rest mass of the electron. In the non-relativistic theory, only the leading
term of this is considered to be the kinetic energy. If one were to expand this to order
(v/c)2 in the velocity, one would get

1 p 2 c2 1 p 4 c4
T ≈ mc2 (1 + − + . . .) − mc2
2 m2 c4 8 m4 c8
p2 1 p4
= − + ...
2m 8 m3 c2
Thus, the first significant term in the kinetic energy, after the non-relativistic expression
1 p4
given by the first term of above, is − , which leads to a reduction in the calculated
8 m3 c2
energy. We will treat this term in the first order of perturbation and calculate the change
in the energy of the state | n, l, mi. The correction to the energy is given by

p4
∆E1 = −hn, l, m | | n, l, mi
8m3 c2
1
=− hn, l, m | p4 | n, l, mi (1)
8m3 c2
We can take the hydrogen atom wavefunctions and operate ∇2 operator on it and calculate
p2
the resulting matrix element. However, there is a smarter way. observing that =
2m
e2
H0 + , we have,
r
e2 e2
   
2
p | n, l, mi = 2m H0 − | n, l, mi = 2m En − | n, l, mi
r r

Thus
2
e2

1
∆E1 = − hn, l, m | En − | n, l, mi
2mc2 r
 
1 2 2 1 4 1
=− En − 2En e h i + e h 4 i (2)
2mc2 r r

The expectation values of the right hand side of (2) can be calculated using,

e2
En =
2a0 n2
1 1
h i= 2
r n a0
1 1
h 2i = (3)
r 1
n3 a20 (l + )
2
Using these, (2) can be simplified as follows :
 
En2  2 e2 e4 1
∆E1 = − 1 − +

2mc2

En n2 a0 En2 1 
n3 a20 (l + )
 2 
En2  4a0 n2 e2 4a20 e4 n4 1
=− 1 − +

2mc2

e2 n2 a0 e4 1 
n3 a20 (l + )
  2

En2  4n 
=− 1 − 4 + (4)
2mc2 1 
(l + )
2
The factor in front of the bracket of (4) can be written as follows :
En2 e2 1
2
= En
2mc 2a0 n 2mc2
2

me4 1
= En 2 2
2~ n 2mc2
α2
= En 2 (5)
4n
where we have defined the fine structure constant α to be
e2 1
α= '
c~ 137
. Using these in (4) we get, the relativistic correction to be given by
 
α2  n 3
∆E1 = −En −  (6)
n2
 1 4
(l + )
2

1.2 Spin-Orbit Interaction

The second correction that we consider is also of relativistic in nature. The origin of spin
orbit interaction can be understood as follows. When an electric charge moving with a
~ it experiences an effective magnetic field, given
speed ~v is subjected to an electric field E,
by
~ = 1 ~v × E
B ~
c
In the present case, the electron is subjected to a Coulomb field due to the proton (which,
in electron’s frame of reference, is moving with a velocity −~v , which makes this effective
magnetic field to be given by
B~ = − e ~v × ~r (7)
cr3
where e is the magnitude of the electronic charge. [ A very pedantic derivation of (7) is
to consider that in the electron’s frame of reference, the proton is moving with a velocity
−~v . This is equivalent to a current I. If one considers a model in which this current is
circulating in a circle of radius r, the magnetic field at the centre of the circle is given by
Biot Savart’s law as
Id~l × ~r
I
1
B=
c r3
The direction of d~l is along that of ~v and the integral is only over the polar angle θ as r
is constant. Recognizing the current I to be e/T = ev/2πr the relation (7) follows.]
The interaction of the magnetic moment of the electron with this magnetic field gives an
interaction energy
~ = eµ ~ · ~v × ~r e ~
V = −~µ · B = − ~ ·L
µ (8)
c r3 mcr3
 ~ = ~r × p~ is the orbital angular momentum of the electron. Writing the magnetic
where L
moment of electron in terms of electron spin, we have
e ~
~ =−
µ S
mc
The interaction energy for the spin-orbit coupling becomes
e2 ~ ~
V = L·S (9)
m2 c2 r3
The observed spin-orbit coupling happens to be half of the value given by (9) because of
spin precession (Thomas precession). Derivation of this requires relativistic transforma-
tion equations and we will simply assume the spin-orbit interaction to be given by the
expression
e2 ~ ~
Vls = L·S (10)
2m2 c2 r3
We will use perturbation theory to obtain the energy correction. However, we also need
to include spin eigenfunctions. It is convenient to take the basis state as those labelled
~ ·S
by J 2 , Jz , L2 and S 2 rather than L2 , Lz , s2 and Sz because L ~ commutes with J 2 and Jz
but does not do so with Lz and Sz . If the second set is chosen, we will additionally need
to diagonalize H0 as well.
Using the first order perturbation theory, we get
e2 1 1 2
∆E2 = h i hJ − S 2 − L2 i
2m2 c2 r3 2
e2 ~2 1
= h i[j(j + 1) − l(l + 1) − −s(s + 1)]
4m2 c2 r3
Let us calculate the factor in the bracket first. We know that corresponding to orbital
angularv momentum l, there are two possible states j = l ± 1/2.
For j = l − 1/2 :

j(j + 1) − l(l + 1) − s(s + 1) = (l − 1/2)(l + 1/2) − l(l + 1) − 3/4 = −(l + 1)

For j = l + 1/2

j(j + 1) − l(l + 1) − s(s + 1) = (l + 1/2)(l + 3/2) − l(l + 1) − 3/4 = l

The expectation value of 1/r3 in the states (n, l, m) is

1 2
h 3
i= 3 3
r a0 n l(l + 1)(2l + 1)
Thus  1 1
if j = l +
e2 ~2

(l + 1)(2l + 1) 2

∆E2 = 1 1
2m2 c2 a30 n3 
− if j = l −
l(2l + 1) 2
The factor on the right hand side can be written as follows :

e2 ~2 e2 ~2 n
=
2m2 c2 a30 n3 2a0 n2 m2 c2 a20 n2
α2
= En 2 n
n
Thus
1  1
if j = l +
α2

∆E2 = En 2 n (l + 1)(2l + 1) 2

1 1 (11)
n  − if j = l −
l(2l + 1) 2
In terms of the j value we may write
 n 1
2 
 if j = l +
α (j + 1/2)(2j) 2
∆E2 = En 2 n 1 (12)
n  − if j = l −
(j + 1/2)2(j + 1) 2

Similarly, the expression (6) can be written as

n 3 1

α2  j − 4 if j = l +
2
∆E1 = −En 2 n 3 1 (13)
n  − if j = l −
j+1 4 2

The total fine structure correction is obtained by adding (12) and (13)

α2 3
 
n
∆E = ∆E1 + ∆E2 = En 2 − (14)
n 4 j + 1/2

3s,3p,3d
3d 5/2
3p3/23d 3/2
3s 3p
1/2 1/2

2s,2p
2p
3/2
2s 2p
1/2 1/2

1s
1s1/2

Figure 1: Fine Structure in Hydrogen Atom

 Quantum Mechanics - II
Approximation Methods :
Perturbation Theory -IV
Zeeman Effect
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
September 30, 2019

1 Introduction
When we put an atom in a magnetic field, the moving charges therein experience Lorentz
force. The interaction of the external magnetic field with the magnetic moment of the
electron gives rise to shift and splitting of the energy levels, known as the Zeeman effect.
A uniform magnetic field B ~ can be expressed by a vector potential A, ~ given by A~ =
1 ~
(B × ~r). Neglecting electron spin for the moment, the Hamiltonian of the hydrogen
2
atom in the magnetic field is given by
1  e ~ 2
H= p~ − A + V (r)
2m c
p2 e 2 2
~ · p~) + e A
~+A
= + V (r) − (~p · A (1)
2m 2mc 2mc2
Note that
~ | ψi = −i~∇
p~ · A ~ ·A~ | ψi
~ · A)
= −i~(∇ ~ | ψi − i~A
~·∇
~ | ψi

1
In Coulomb gauge ∇ ~ ·A~ = 0 and we can, therefore, replace p~ · A
~ by A
~ · p~ in (1). Further,
~ · p~ may be expressed in terms of the orbital angular momentum of the electron
the term A
as,

~ · p~ = 1 (B
A ~ × ~r) · p~
2
1~
= B · (~r × p~)
2
1~ ~
= B ·L (2)
2
Using this, the Hamiltonian (1) may be expressed as

p2 e ~ ~ e2 A2
H= + V (r) − B·L+ (3)
2m 2mc 2mc2
To this, we can add the interaction of electron spin magnetic moment with the magnetic
field
~ ·B
µ ~ =− e B ~ ·S ~ (4)
mc
If we take the magnetic field along the z− direction, we could choose a gauge in which
the vector potential is given by
A~ = B (xĵ − y î)
2
In addition, we can include the spin-orbit interaction term Hs.o. . The final Hamiltonian
becomes
p2 e e2 A2
H= + V (r) + Hs.o. − B(Lz + 2Sz ) + (5)
2m 2mc 2mc2
The last term gives diamagnetic effect and is generally too small even for moderate
strengths of the magnetic field. We will neglect this term. The Zeeman term is given
by the penultimate term. If the spin is neglected, the corresponding effect is called the
normal Zeeman effect while the inclusion of spin gives rise to what is termed as the
anomalous Zeeman effect.
We will treat the Zeeman term in the perturbation theory. This requires us to evaluate
the expectation value of Lz + 2Sz in the unperturbed states of the system. We have seen
earlier that when the spin-orbit term is included, the angular momentum representation
{j, m, l, s} is better suited for calculation. Let us write Lz + 2Sz = Jz + Sz . We have

hj, m | Jz + Sz | j, mi = m~ + hj, m | Sz | j, mi (6)

2
In order to evaluate the second term on the right, we need to go over to the uncoupled
representation {l, s, ml , ms }. We have
1 1 1 1
| j = l + , m = l + i ≡| l, ; l, i
2 2 2 2
Apply J− on the left and L− + S− on the right to get
√ 1 1 √ 1 1 1 1
2l + 1 | j = l + , m = l − i = 2l | l, ; l − 1; i+ | l, ; l; − i
2 2 2 2 2 2
i.e. r r
1 1 2l 1 1 1 1 1
| j = l + ,m = l − i = | l, ; l − 1; i + | l, ; l; − i
2 2 2l + 1 2 2 2l + 1 2 2
Using a recursion, we get for j = l + 1/2
v v
ul + 1 + m ul + 1 − m
u u
1 t
2 1 1 t 2 1 1
| j = l + , mi = | ml = m − , ms = i+ | ml = m + , ms = − i
2 2l + 1 2 2 2l + 1 2 2
(7)
and for j = l − 1/2
v v
u 1
ul + − m ul + 1 + m
u
1 t
2 1 1 t
2 1 1
| j = l − , mi = | ml = m − , ms = i+ | ml = m + , ms = − i
2 2l + 1 2 2 2l + 1 2 2
(8)
1
Using these, we get for j = l + ,
2
1 1
~l+ 2 +m ~l+ 2 −m m~
hj, m | Sz | j, mi = − = (9)
2 2l + 1 2 2l + 1 2l + 1
1
and for j = l − ,
2
m~
hj, m | Sz | j, mi = − (10)
2l + 1
Substituting the above in Eqn. (6), we get for the Zeeman energy,

m 2l + 2 1
| e | B~ m + 2l + 1 = 2l + 1 m for j = l +

∆E = 2 (11)
2mc  m 2l 1
m − = m for j = l −
2l + 1 2l + 1 2

3
Since m takes 2j + 1 values, the states are split into 2j + 1 equally spaced levels.
Consider the Zeeman splitting of n = 1 and n = 2 levels of hydrogen atom. We start
with the unperturbed energy levels after including the spin-orbit interaction. The 1s1/2
has j = l + 1/2 = 1/2 with l = 0. Thus ∆E = µB Bm where µB = (e~/2mc) is the Bohr
magneton. The energy level splits into two levels with m = ±1/2 with separation 2µB B.

2p3/2

4µB B/3

2s1/2 2p1/2

2µB B/3

1s1/2
2µB B

Figure 1: Zeeman splitting in n = 1 and n = 2 levels of Hydrogen (not to scale)

The doubly degenerate 2s1/2 and 2p1/2 are split as follows :

2s1/2 has l = 0, j = 1/2 = l + 1/2, so that the change in the energy is given by ±µB B
as in the case of 1s1/2 . For the p-state we have l = 1, j = 1/2 = l − 1/2 so that the

4
appropriate energy expression is that given by the second case of (11),

2 1 µB B
∆E = µB B (± ) =
3 2 3
The four energy states are thus lowered by −µB B, −µB B/3, +µB B/3, +µB B. The spacing
between the energy levels is 2µB B/3.
Finally, 2p3/2 has l = 1, j = 3/2 = l + 1/2 and ∆E = 4µB B/3. The energy levels are
shown in Fig. 1.

5
 Quantum Mechanics-II
Approximation Methods :
(Variational Principle)
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai
October 21, 2018

1 Introduction
Variational method is often used to provide an upper bound of the ground
state energy of a system where exact solution is not feasible. Alternatively,
it is also useful for systems where perturbation theory cannot be applied
because we do not have a knowledge about a closely related Hamiltonian
whose exact solution is not known.

2 Upper Bound for the Ground State Energy

Consider an arbitrary state | ψi, known as the trial state. It can be shown
that the expectation value of the Hamiltonian in such a trial state is always
greater than (or at best equal to) the true ground state energy. Let {| φn i}
be a complete set of eigenstates of the Hamiltonian with the corresponding
eigenvalues {En }, where the energies are arranged in ascending order with
E0 ≤ E1 ≤ E2 ≤ . . .. We expand the trial state in terms of this complete set
of eigenfunctions X
| ψi = an | φn i (1)
n

1
The expectation value of the Hamiltonian in the trial state is
hψ | H | ψi
E[ψ] = (2)
hψ | ψi
P∞
|an |2 hφn | H | φin
= n=0 P∞ 2
n=0 |an |
P∞ 2
n=0 En |an |
= P ∞ 2
n=0 |an |
∞
|an |2
P
≥ E0 Pn=0
∞ 2
= E0 (3)
n=0 |an |

The physical reason is clear. It simply states that the expectation value
(which is essentially an average), cannot be lower than the lowest of the
energies, i.e., ground state energy. The difference E[ψ] − E0 is given by
P∞
|an |2 (En − E0 )
E[ψ] − E0 = n=1P∞ 2
(4)
n=0 |an |

This tells us that if the overlap between the trial state and the eigenstate
of the Hamiltonian for n 6= 0, i.e. for states other than the ground state, is
O(), the ground state energy differs from the variational estimate by O(2 ).
Another way of stating the variational principle is to say that the energy value
is stationary with respect to a δ− variation of the trial wavefunction. Before
establishing this result, let us recapitulate our idea about what is meant by
a functional. Here we have to determine the state | ψi which optimises the
energy E[| ψi], which depends on | ψi itself. The way it has been written
seems to suggest that E[ψ(x)] is nothing but function of a function However,
there is a subtle difference between a functional and function of a function.
A function is a one to one mapping from a range of values in its domain to
a value in its range. A functional takes as its argument, not one particular
value but a function itself and maps it to a definite value. For different
functions (states) as its argument, the functional returns a different value.
Let | ψi be a trial wavefunction and E[ψ] be the expectation value of the
Hamiltonian in this state. If | δψi is a small variation to the state vector,
the change in energy is given by
δE[ψ] = E[ψ + δψ] − E[ψ]
hψ + δψ | H | ψ + δψi hψ | H | ψi
= −
hψ + δψ | ψ + δψi hψ | ψi

2
We expand the above, keeping terms up to fist order in | δψi

hψ | H | ψi + hψ | H | δψi + hδψ | H | ψi hψ | H | ψi
δE[ψ] =   − (5)
hδψ | ψi hψ | δψi hψ | ψi
hψ | ψi 1 + +
hψ | ψi hψ | ψi

Keeping terms up to first order in δψ, the first term in (5) may be simplified
as follows:
 
hψ | H | ψi + hψ | H | δψi + hδψ | H | ψi hδψ | ψi hψ | δψi
δE[ψ] = 1− −
hψ | ψi hψ | ψi hψ | ψi
hψ | H | ψi hψ | H | ψi hδψ | ψi hψ | H | ψi hψ | δψi
= − −
hψ | ψi hψ | ψi hψ | ψi hψ | ψi hψ | ψi
hψ | H | δψi hδψ | H | ψi
+ + (6)
hψ | ψi hψ | ψi

Substituting (6) in (5), and using (2) we get,

hψ | δψi hδψ | ψi hψ | H | δψi hδψ | H | ψi

δE[ψ] = −E[ψ] − E[ψ] + + (7)
hψ | ψi hψ | ψi hψ | ψi hψ | ψi

Thus, E is stationary if δE[ψ] = 0, i.e.

H | ψi = E[ψ] | ψi (8)

The equation (8) is just the Schrödinger equation satisfied by H. Thus the
eigenvalues of H can be obtained by finding the stationary values of E[ψ]
with respect to the variation in | ψi, subject to the constraint hψ | ψi being
constant. Even with a rough value of | ψi, we can get a good estimate of E
because the error in the energy is second order in δψ.
To use variational principle, we first make an educated guess of the trial
wavefunction, which takes into the properties of the wavefunction that we
are sure about, e.g., symmetry properties, asymptotic behaviour, number of
nodes etc. To take into account other properties that we do not have an
information on, we include adjustable parameter(s), say, {βi } so that the
trial wavefunction is written as dependent on such parameters, viz., ψtrial =
ψt (β1 , β2 , . . . , βN ). We then calculate energy by the expression

hψt (β1 , β2 , . . . , βN ) | H | ψt (β1 , β2 , . . . , βN )i

E(β1 , β2 , . . . , βN ) =
hψt (β1 , β2 , . . . , βN ) | ψt (β1 , β2 , . . . , βN )i

3
We then minimise the energy functional by the condition
∂E
= 0, (for βi = 1, 2, . . . , βN )
∂βi
This determines the set β10 , β20 , . . . , βN 0 , which minimises the energy.

3 Energy of the First Excited State

Having discussed the recipe for the variational ground state energy, let us
consider how to get an estimate of the approximate energy of the first excited
state. Choose a trial function | ψ1 (β)i which is normalized and is orthogonal
to the true ground state function | ψ0 i. An upper bound for the first excited
hate of the Hamiltonian is obtained as follows:
hψ1 | H | ψi1
E1 [β] =
hψ | ψ1 i
P 1
hψ1 | H | φm ihφm | ψ1 i
= m
hψ1 | ψ1 i

where in the last expression, we have introduced a complete set of orthonor-

mal eigenfunctions of the Hamiltonian. We then have
X
E1 [β] = Em |hψ1 | φm i|2
m
N
X −1
= 0 + E1 + |hψ1 | φm i|2 Em
m=2
≥ E1

This works well when we know the true ground state. However, if we only
have a variational estimate of the ground state the orthogonality condition
may not be exact, in whch case, the error in the energy of the excited state
is larger than that in the calculation of the ground sate. It is of course
possible that the ground state and the first excited state may have different
symmetry which may still guarantee strict orthogonality. For instance, in
one dimension systems with symmetric potential (e.g. harmonic oscillator,
particle in a box with the origin chosen at the centre of the well), the ground
state is even function of x while the first excited state is an odd function.

4
Thus any trial function, which is odd function of x will serve well. This will
then provide a good estimate of the excited state energy.
An identical procedure may be used to obtain estimate of second and higher
excited states. Suppose for the (n + 1)-th state, we choose a function | φi
which is orthogonal to all the lower states,

hφ | ψ0 i = hφ | ψ1 i = hφ | ψ2 i = · · · = hφ | ψn i = 0

Then hφ | H | φi provides a good estimate of the energy of this state.

Like in the case of the first excited state, it is occasionally possible to choose
an appropriate trial wavefunction for such states as well. For instance, for
spherically symmetric potentials, angular momentum l is a good quantum
number. Since states of different l are orthogonal, we may get an estimate of
the lowest energy corresponding to a particular value of l by choosing a trial
wavefunction with Ylm as a factor.

4 Properties of the Ground state for one di-

mensional potentials
Frequently, we are interested in getting estimates for the ground state energy
for potentials in one dimension. Several rigorous theorems are useful in
choosing trial wavefunctions in such situations. In this section, we discuss
properties of one dimensional systems which are useful in choosing a trial
wavefunction.
Theorem: For velocity independent potentials, the ground state wave-
function is nodeless.
Proof: A rigorous proof of this statement is beyond the scope of our course.
(One dimensional Schrödinger equation is an example of Sturm-Liouville
problem and the proof depends on the solution of such problems.) However,
we start with a simple intuitive proof of the theorem, following it up with
a proof based on variational principle. Let us assume that the problem has
at least one bound state, so that the potential energy term is negative. We
can then reduce the total energy by reducing the kinetic energy term. Now,
kinetic energy is proportional to the curvature of the wavefunction, and can
thus be reduced by reducing the curvature. Now a nodeless function, obvi-
ously, has less curvature than any function which crosses the abscissa. Hence,
the energy of a function with a node is greater than that which is nodeless.

5
In the following we sketch a mathematical proof based on this principle. If
you consider it too mathematical, you may skip it
Kinetic energy is given by
Z ∞ 2
~2 d ψ(x)
T =− dx (9)
2m −∞ dx2
Integrating successively by part twice, we have
Z ∞ ∞ Z ∞
d2 ψ(x) dψ ∗ (x) dψ(x)

∗ ∗ dψ(x)
ψ (x) dx = ψ (x) − dx
−∞ dx2 dx −∞ −∞ dx dx
Z ∞
dψ ∗ (x) dψ(x)
=− dx (10)
−∞ dx dx
∞ Z ∞
dψ ∗ (x) d2 ψ ∗ (x)

= − ψ(x) + ψ(x) dx
dx −∞ −∞ dx2
Z ∞
d2 ψ ∗ (x)
= ψ(x) dx (11)
−∞ dx2
Where (10) and (11) are respectively obtained from the immediately pre-
ceding expression by the condition that the wavefunction and its derivative
must vanish at ±∞. Using equations (9), (10) and (11), we may write the
expression for the kinetic energy in a symmetric form
Z ∞
~2 d2 ψ(x) d2 ψ ∗ (x) dψ ∗ (x) dψ(x)

∗
T =− ψ (x) + ψ(x) −2 dx (12)
8m −∞ dx2 dx2 dx dx
Let us write the form of the wavefunction as
ψ(x) = f (x)eiφ(x) (13)
where we choose f (x) ≥ 0. With this form, we have
dψ(x) df dφ
= eiφ + f ieiφ (14a)
dx dx dx
dψ ∗ (x) df dφ
= e−iφ − f ie−iφ (14b)
dx dx dx
2 2
 2 2
dψ iφ df dφ iφ d f iφ dφ iφ d φ
= 2ie + e − e f + ie f (14c)
dx2 dx dx dx2 dx dx2
 2
d2 ψ ∗ −iφ df dφ
2
−iφ d f −iφ dφ 2
−iφ d φ
= −2ie + e − e f − ie f (14d)
dx2 dx dx dx2 dx dx2

6
The first pair of equations (14a) and (14b) may be multiplied to give
2 2
dψ(x) dψ ∗ (x)
 
df 2 dφ
= +f (15)
dx dx dx dx

From (14c) and (14d) we get (by multiplying (14c) by ψ(x) = f (x)eiφ and
(14d) by ψ ∗ (x) = f (x)e−iφ and adding the resulting equations)
2
d2 ψ ∗ d2 ψ d2 f

dφ
ψ(x) 2 + ψ ∗ (x) 2 = 2f 2 − 2f 2 (16)
dx dx dx dx

Integrating equation (16) and integrating the first term on the right by parts,
df
and, using the fact that both f (x) and vanish at ±∞, we get
dx
Z ∞ Z ∞  2  2
d2 ψ ∗ ∗ d2 ψ 2 dφ df
[ψ(x) 2 + ψ (x) 2 ]dx = −2 [f + ]dx (17)
−∞ dx dx −∞ dx dx

The right hand side of (17) is identical to the integral of (15) so that when
these are substituted in (12), we get
∞ 2 ∞ 2
~2 ~2
Z  Z 
df 2 dφ
Ekin =+ dx + f dx (18)
2m −∞ dx 2m −∞ dx

Since kinetic energy is positive, we may reduce its value by a proper choice
dφ
of the second term, viz., by choosing = 0, which implies φ = constant.
dx
However, a constant phase in the wavefunction has no physical significance
and we may, therefore, take φ = 0. Thus the wavefunction is f which is
positive by choice, which shows that the ground state has no node.
Corollaries

1. The ground state for a one dimensional potential is non-degenerate.

If it were degenerate, there would be another wavefunction having the
same energy but orthogonal to the ground state. Since neither function
can change sign, it is not possible.

2. The ground state has angular momentum l = 0. States of nn-zero l are

2l + 1 fold degenerate, which is not possible by corollary 1.

7
 ∞ ∞

∞ ∞
x
−a +a

V (x) x
−a +a

Figure 1: Left: An arbitrary attractive potential and a superposed box poten-

tial. Right: Eigenstates of box potential, the number of nodes is independent
of the box width.

3. If the Hamiltonian is invariant under parity transformation, i.e. if

H(−x) = H(x), since the ground state does not change sign ψ(−x) =
ψ(x). Note that if V (−x) = V (x), i.e. the Hamiltonian is symmet-
ric, by letting x → −x, we find that ψ(−x) is also a solution to
the Schrödinger equation. However, since the ground state is non-
degenerate, ψ(x) and ψ(−x) must represent the same wavefunction. If
ψ(−x) = −ψ(x) it would imply a node at x = 0.
4. The n−th state of the system has exactly n − 1 nodes, with one node
between the n−th and (n + 1)-th state. Proof of this requires a bit of
explanation.

We start with an intuitive proof 1 . Consider a potential V (x) given in the

figure below. Let us also consider an auxiliary potential defined by
(
V (x) for − a ≤ x ≤ a
Vnew (x) = (19)
∞ for |x| ≥ a
If a is sufficiently small, the floor of the new potential is approximately flat
and Vnew (x) may be considered to be a particle in a box problem. The
1
: Reference : N. Moriconi, Am. J. Phys. 75, 284 (2007); arXiv:quant-ph/0702260

8
 ∞ ∞

x
−a +a

Figure 2: Showing the ground state wavefunction with a node required at an

end to create a new node. The red coloured bend shows that the slope must
change sign.

eigenstate of the particle in a box problem are exactly known. The n−th
eigenstate has (n − 1) nodes, irrespective of the width of the box. Starting
with any of the eigenfunctions, if we move the walls of Vnew (x) outward,
the potential would resemble the given potential V (x) and the wavefunction
would be a better approximation to the wavefunction corresponding to the
original problem with potential V (x). The question now is, can an additional
node appear as we move the walls of the box outward? We know that the
solutions of Schrödinger equation as a function of parameter a as to develop
continuously and no node can suddenly appear or get destroyed. Thus can
such a wavefunction develop an extra node between ±a as a function of the
wall separation?

Consider the situation shown in Figure 2. We have shown the ground

state wavefunction for simplicity but similar argument would hold good for
the higher states as well. In this case the wavefunction goes to zero at the
right wall with a negative slope. In order that an additional node develops,
it must turn around to a positive slope, as shown (with a red coloured bend
near the wall). This means that the slope must reduce to zero before turning
around. However, as the wavefunction vanishes there, it means that both ψ
dψ
and become zero. Now Schrödinger equation is a second order differential
dx
dψ
equation, whose solutions are initiated by values of ψ(x) and at a point.
dx

9
If both these are zero at the same point, the solution is identically zero
everywhere.
A second possibility is that a double zero appears between −a and +a, so
ψ
that a turn around is not required. However, a double zero implies = 0,
dx
which leads us to the same conclusion. Thus no new node can be created or
destroyed.
To get a little more analytical insight, suppose u1 and u2 are two independent
solutions of the same Schrödinger equation

~2 d2 u
− + V (x)u = Eu
2m dx2
Since they correspond to the same energy E , we have

~2 d2 u1
− + V (x)u1 = Eu1 (20)
2m dx2
~2 d2 u2
− + V (x)u2 = Eu2 (21)
2m dx2
Multiply (20) bu u2 and (21) by u1 and subtract. We get

dW
u1 u002 − u2 u001 = 0 =
dx
where W is the Wronskian of the solution
u1 u2
W = u1 u02 − u2 u01 = (22)
u01 u02

which is a constant since dW/dx = 0. Suppose, due to some boundary

conditions at some point x (which could be even x → ±∞), both u1 and
u2 vanish, the Wronskian being a constant must have zero value everywhere.
and we have
u01 u0
= 2
u1 u2
that is, the logarithmic derivatives of both the functions are equal. Inte-
grating, we get u1 = ec U2 , where c is a constant. Since two wavefunctions
which differ by a constant phase represent the same state, the ground state
is non-degenerate.

10
 Theorem
Between two successive zeros of | ψn i, there is a zero of | ψm i for any m > n.
Proof :
In this case the Wronskian is given by
dW
= (ψn0 ψn − ψm 0
ψn )0 = (Em − En )ψn ψm (23)
dx
Suppose ψn has two successive zeros between x1 and x2 . We may assume
ψn to be positive in this interval x1 < x < x2 , if not the wavefunction could
be multiplied by a minus sign. Hence ψn0 (x1 ) > 0 and ψn0 (x2 ) < 0. If we
integrate (23), we get
Z x2
0 0
ψn (x2 )ψm (x2 ) − ψn (x1 )ψm (x1 ) = (Em − En ) ψn (x)ψm (x)dx
x1

If ψm (x) does not vanish in the interval x1 < x < x2 , we can assume ψm (x)
also to be positive in this interval. But then left side of the above equation is
negative, while the right hand side is positive leading to a contradiction.

5 Applications
5.1 The Deuteron Problem
The deuteron is bound by short range attractive nuclear force. A reasonable
model for the potential is given by V = −Ae−r/a , where, phenomenologically.
A ' 32 MeV and a ' 2.2 fm. To estimate the binding energy, we consider
a trial wavefunction which has similar features, viz., it peaks at the origin
and falls off exponentially thereafter. A normalized, trial wavefunction with
a single parameter β is chosen to be
 3 1/2
β
ψ(β) = e−βr/2a (24)
8πa3
Since the wavefunction depends only on the radial coordinates, we take the
Hamiltonian to be
~2 2
H=− ∇ − Ae−r/a
2m
~2 1 d
 
2 d
=− 2
r − Ae−r/a (25)
2m r dr dr

11
Using (24), we have

E[β] = hψ(β) | H | ψ(β)i

 3  2 Z ∞  3  Z ∞
β ~β −β/a β
= 3
4π 2
(2r − r (β/2a))e dr − A 3
4π r2 e−r(1+β)/a dr
8πa 4ma 0 8πa 0
~2 β 4 β 3 2a3
 
2 2
= − (β/2a) −A 3
8ma4 (β/a)2 (β/a)3 2a (1 + β)3
~2 β 2 β3
= − A
8ma2 (1 + β)3

Minimizing E[β] with respect to β, we get an equation

(1 + β)4 12mAa2
=
β ~2
Substituting for m the reduced mass of neutron-proton system and the phe-
nomenological values of A and a given earlier, we find the value of β which
optimizes energy to be 1.34 and the corresponding binding energy to be −2.12
MeV, which compares favourably with the actual binding energy −2.245
MeV.

5.2 The Infinite Potential Well

The problem of a particle in an infinite potential well is of course an exactly
solvable problem. However, we will attempt to get an estimate of the bound
state energy by taking a trial wavefunction which has the property that it
has node(s) at x = ±a. Let us take

ψ(β) = aβ − |x|β (26)

Since the chosen function is even, the normalization gives
Z a
hψ(β) | ψ(β)i = 2 (aβ − xβ )2 dx
Z0 a
=2 (a2β + x2β − 2aβ xβ )dx
0
β2
= 4a2β+1 (27)
(2β + 1)(β + 1)

12
Thus, the normalized wavefunction is given by
s (
(β + 1)(2β + 1) aβ − (−x)β for x < a
ψβ (x) = (28)
4β 2 a2β+1 aβ − x β for x > a

The energy, which is just the kinetic energy within the well is calculated as
follows.
Z 0
~2 (β + 1)(2β + 1) β β d
2
E[β] = − [a − (−x) ] [aβ − (−x)β ]dx
2m 4β 2 a2β+1 −a dx 2
Z a 2

β β d β β
+ [a − x ] 2 [a − x ]dx
0 dx
2 Z a 2
~ (β + 1)(2β + 1) β β d
=− 2 [a − x ] [aβ − xβ ]dx
2m 4β 2 a2β+1 dx 2
2 Z a0
~ (β + 1)(2β + 1)
=− 2 2β+1
[aβ − xβ ](−β)(β − 1)xβ−2 dx
m 4β a 0
2
~ (β + 1)(2β + 1) β
= 2 2
β(β − 1)
ma 4β (β − 1)(2β − 1)
2
~ (β + 1)(2β + 1)
= (29)
4ma2 2β − 1

Minimizing E[β] with respect to beta gives (ignoring the negative value of
β, as it would make the wavefunction diverge at x = 0), we get
√
1+ 6
β= ' 1.72 (30)
2
The variational estimate of the energy is

~2
E = 4.95 (31)
4ma2
against the exact value
π 2 ~2
E= (32)
8ma2
which is 99.7% of the variational estimate.
To see how well the variational wavefunction mimics the actual wavefunc-
tion, we could evaluate the overlap between the trial wavefunction and the

13
actual wavefunction explicitly. However, note that if we assume that the
variational state | gi is normalized, we can write, introducing a complete set
of eigenstates of H,

Emin = hg | H | gi
X
= hg | mihm | H | nihn | gi
m,n
X
= |hg | ni|2 En
m
≥ |hg | 0i|2 E0 + 9E0 (1 − |hg | 0i|2 )
= −8E0 |hg | 0i|2 + 9E0 (33)

The penultimate line follows because (i) the term hg | 1i vanishes as the
two states have opposite parity, the first non-vanishing state is |h0 | 2i|2 9E0 ,
where the second excited state | 2i has an energy E2 = 9E0 and (ii) since
X X
hg | gi = 1 = hg | nihn | gi = |hg | ni|2
n n
X
2 2
= |hg | 0i| + |hg | 2i| + |hg | ni|2
n>2

so that
|hg | 2i|2 < 1 − |hg | 0i|2
and
9E0 − Emin
|hg | 0i|2 ≥ ' 0.9996
8E0

5.3 Application to Helium Atom

We had earlier applied Rayleigh Schrödinger perturbation theory to the prob-
lem of Helium atom. We found that within the perturbation framework, the
electron-electron interaction accounts for an energy difference of 5Z/4 = 2.5
Rydbergs, which, when added to the energy −2Z 2 = −8 Rydbergs of two in-
dependent hydrogen-like atom s with Z = 2 gives an energy of −5.5 Rydbergs
= −74.8 eV, which compares favourable with the experimentally determined
value of −78.98 eV.
The estimate can be improved further by observing that each electron in He-
lium atom actually sees somewhat reduced nuclear charge due to screening

14
of the same by the electron. Thus the single electron wavefunction is charac-
terised by an effective charge Z 0 , instead of Z, where this Z 0 is the variational
parameter. Note that in the Hamiltonian, the charge that the electron sees
is still Z because the electron electron interaction term is explicitly included,
which results in Z 0 appearing in the wavefunction. We, therefore take the
electron wavefunction to be given by
1/2
Z 03

0
ψ(r1 ) = ψ100 = e−Z r1 /a0 (34)
πa30

and a similar equation for ψ(r2 ).

It is not necessary to solve the Schrödinger equation anew for the single
electron problem. We need to do some smart mapping. Recall that the
single electron Hamiltonian is given by

p2 Ze2
H= − (35)
2m r
We may rewrite (35) as

p2 Z 0 e2 (Z 0 − Z)e2
H= − + (36)
2m r r
The one electron energy is given by

p2 Z 0 e2 (Z 0 − Z)e2
hψ100 | H0 | ψ100 i = hψ100 | − | ψ100 i + hψ100 | | ψ100 i
2m r r
(Z 0 − Z)e2
= −Z 02 E0 + hψ100 | | ψ100 i
r
where, as before, E0 = 1 Ry. The first matrix element on the right of above
equation gives −Z 02 Ry. because the matrix elements are taken between
hydrogen - like wavefunctions with the nuclear charge equal to −Z 0 both in
the wavefunction and the Hamiltonian. The second matrix element requires
an explanation. Note that the wavefunction has Z 0 as the nuclear charge.
Hence, if we had taken the matrix element of Z 0 e2 /r between these these
states, it would have simply given the magnitude of the potential energy
of the hydrogen-like atom with nuclear charge Z 0 , which would have been
Z0 − Z
2Z 02 Ry. Thus the value of the second matrix element is × 2Z 02 =
Z0

15
(Z 0 − Z)2Z 0 E0 . The contribution to the one electron energy from these two
electrons is thus

E1 = −2Z 02 E0 + 4(Z 0 − Z)Z 0 E0 = (2Z 02 − 4ZZ 0 )E0 (37)

We now add to this the electron-electron interaction term, which we will take
to be what was calculated in perturbation theory, with the difference that we
replace Z be Z 0 because the electron-electron interaction did not have any
reference to Z while our trial wavefunction contains a Z 0 instead of Z. Thus
the variational energy is

5Z 0
E[Z 0 ] = (2Z 02 − 4ZZ 0 + )E0 (38)
4
Minimizing this expression, we get
5
Z0 = Z −
16
Substituting this in the expression for the energy, we get the variational
ground state energy to be 5.695 Ry=77.4 Ry.

5.4 Application to 3-d Harmonic Oscillator

3-d harmonic oscillator is an exactly solvable problem with a non-degenerate
ground state having an energy 3~ω/2 and the wavefunction is given by
 mω 3/4 mω 2 r
| ψg i = exp(− ) (39)
π~ 2~
The oscillator potential is mω 2 r2 /2. Let us consider a trial wavefunction
2
ψt = N e−βr (40)

The trial wavefunction has correct limiting behaviour at ±∞. The normal-
 3/4
2β
ization constant can be calculated easily and is given by N = . The
π

16
kinetic energy term is calculated as follows :
3/2 ∞
~2
 Z  
2β −βr2 1 d 2d −βr2
Ekin =− 4π e r e dr
2m π 0 r2 dr dr
3/2 Z ∞
~2

2β 2
=− 4π(−2β) e−2βr (3 − 2βr2 )r2 dr
2m π 0
2
 3/2  √ √ 
~ 2β 3 π 3 π
= 8πβ 3/2
− 2β
2m π 4 (2β) 8 (2β)5/2
3~2
= β (41)
2m
The potential energy is seen to be
3/2 ∞
mω 2
 Z
2β 2
Epot = 4π e−2βr r4 dr
2 π 0
2
 3/2 √
mω 2β 3 π
= 4π
2 π 8 (2β)5/2
2
3mω
= (42)
8β

The total energy is obtained by adding (41) and (42)

3~2 3ω 2
E[β] = β+ (43)
2m 8β
Minimizing with respect to the variational parameter β, we get βmin =
mω/2~. Substituting this value in (43) to be

3~ω 3~ω 3~ω

E= + = (44)
4 4 2
The ground state wavefunction is given by

mω 2
 mω 3/4  
ψ(r) = exp − (45)
π~ 2~

which agrees with the exact solution.

17
6 Linear Variation Functions
The principle of the method linear variation function function, used fre-
quently molecular orbital calculations is that, instead of choosing a single
parameter variational function, we choose a trial function which is a linear
combination of a number of linearly independent functions φi (x)
X
ψt (x) = ci φi (x) (46)
i

and determine the coefficients ci by optimization

P 2 of the variational energy,
subject to the normalization constraint i ci = 1. We will assume the
functions to be real, though this constraint is not really necessary. Likewise,
it is not necessary to assume that the functions φi (x) are orthogonal to one
another, though, if they were so, our equations would become much easier
to handle. We will assume that the functions φi (x) need not be orthogonal
nor normalized. The variational energy is given by
P
hψt | H | ψt i i,j ci cj hφi | H | φj i
Etrial = = P (47)
hψt | ψt i i,j ci ci hφi | φj i

The numerator now contains matrix elements of H between the basis states
φi and the denominator contains overlap integrals between these functions.
Had the basis been orthonormal, the overlap integral would be δi,j . Let us
denote the former by Hi,j and the overlap integrals in the denominator by
Si,j ,
Z
Hi,j = φi (x)Hφj (x)dx (48a)
Z
Si,j = φi (x)φj (x)dx (48b)

Using these, the variational energy becomes

P
i,j ci cj Hi,j
Et = P (49)
i,j ci cj Si,j

This energy has to be minimized with respect to the coefficients {ck }, which
requires
∂Et
=0 (50)
∂ck

18
for each ck , since each ck is independent. To do this variation, we first cross
multiply the lhs and rhs of (49) to get
X X
Et ci cj Si,j = ci cj Hi,j
i,j i,j

∂ci
and use = δi,k . We get
∂ck
∂Et X X X
ci cj Si,j + 2Et cj Sk,j = 2 cj Hk,j
∂ck i,j j j

Now, using condition (50) we get, using Hk,j = Hj,k , which follows from the
hermiticity of the Hamiltonian and Sk,j = Sj,k ,
X
cj (Hk,j − Et Sk,j ) = 0 (51)
j

Equation (51) being a coupled homogeneous equation in the coefficients cj s,

the existence of non-vanishing solution requires vanishing of the secular de-
terminant, which provides a solution for the optimized energy.

6.1 An example:
Consider a particle in an infinite potential well with boundaries at x = 0
and x = L. Inside  the box, the particle is subjected to a linear potential
L
V (x) = k x − . Use the trial wavefunction to be a linear combination
2
of the ground and the first excited state of the particle in a box to obtain an
estimate of the variational energy.
Solution: We take the trial wavefunction to be
r r  
2  πx  2 2πx
ψt (x) = c1 sin + c2 sin
L L L L
In this case, since the trial wavefunction chosen is a combination of two
orthonormal wavefunctions, the overlap integral Si,j = δi,j , and the secular
determinant becomes
H11 − Et H12
=0 (52)
H21 H22 − Et

19
 R ∂2
The kinetic energy term φi (x) 2 φi (x)dx is just the energy of the particle
∂x
in a box problem for the ground state and the excited state, giving E0 and
4E0 respectively. The off-diagonal contribution to the kinetic energy is zero
because the second derivative of φi (x) simply gives a constant times the same
φi (x), and, since the functions φ1 (x) and φ2 (x) are orthogonal, the integrals
vanish. We now need to calculate the contribution to the secular determinant
by the potential energy term.
The diagonal contributions to the potential energy requires integrals of the
RL π 2π
type 0 x sin2 (ax)dx where a = for φ1 and = for φ2 . This integral is
L L
evaluated using integration by parts.
1 − cos(2ax) 1 − cos(2ax)
Z Z Z Z
2
x sin (ax)dx = x × dx − [ dx]dx
2 2
Z
x sin(2ax) x sin(2ax)
=x×( − ) − [( − )dx
2 4a 2 4a
x2 x sin(2ax) x2 cos(2ax)
= − − +
2 4a 4 8a2
2
x x sin(2ax) cos(2ax)
= − +
4 4a 8a2
Substituting limits and using the fact that φ1 (x) and φ2 (x) are normalized,
we have
Z L Z L
L 2 2 2 πx
  kL2
k(x − )φ1 (x) = kx sin dx −
0 2 0 L L 2
2 2
2L kL
=k − =0
L 4 2
where we have used the fact that both the sine and the cosine terms give zero.
The diagonal term involving φ2 (x) is also similarly zero. We now calculate
the off diagonal term
Z L Z L
2 L
Z  
L  πx  2πx
k(x− )φ1 (x)φ2 (x)dx = kxφ1 (x)φ2 (x)dx = kx sin sin dx
0 2 0 L 0 L L
the neglected term is zero since φ1 (x) and φ2 (x) are orthogonal. This integral
term is done by first expressing the product of the sine functions as difference
of two cosine terms,
2 L k L
Z  πx    Z     
2πx πx 3πx
kx sin sin dx = x cos − dx
L 0 L L L 0 L L

20
Integration is straightforward,
 
3πx
 πx   
 
sin
k  sin L L
Z Z L  
L  πx  k L L 3πx 
x π |L0 − sin dx − x
  L
|0 − sin dx
L 0 π L L 3π 0 3π L 
L L
 2
k L  πx L
 L2  πx  
= cos | − cos |L
L π2 L 0 9π 2 L 0
16kL
=−
9π 2
Thus the secular equation is

16
E0 − E − 2 kL
9π =0
16
− 2 kL 4E0 − E
9π
which gives
 1/2
2 16kL 2
E = 5E0 ± 9E0 − ( )
9π 2
The lower sign corresponds to the optimized variational energy
 1/2
16kL 2
Emin = 5E0 − 9E02 −( ) (53)
9π 2

21
 Quantum Mechanics-II
Approximation Methods :
(Time Dependent Perturbation Theory)
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai
November 15, 2018

1 Introduction
Till now we have discussed systems where the Hamiltonian had no explicit
time dependence. We will now consider situation where a time dependent
perturbation V (t) is present in addition to the time independent Hamiltonian
H0 , the solution of the latter problem is known to us and its eigenstates are
given by
H0 | φn i = En | φn i (1)
In the absence of the perturbation, if the system initially happened to be in
a particular eigenstate —| ψn i of H0 , it would continue to be in that state
for ever, apart from picking up an unimportant phase factor eiEn t/~ . A time
dependent perturbation would change that and the system would no longer
in that eigenstate but be found in some state | ψ(t)i. Since any arbitrary
state can always be expressed as a linear combination of the complete set
of eigenstates {| φn i} of H0 , it implies that the perturbation induces transi-
tion between different eigenstates. The time evolution operator is no longer
exp iHt/~, as would be the case if H were independent of time. The question
that we address is what is the probability of transition from the given initial
state | ψn i to different eigenstates ψm of the Hamiltonian H0 , where m 6= n
?

2 Schrödinger, Heisenberg and Interaction

Pictures
We start with a review of Schrödinger and Heisenberg pictures, which we had
come across in QM-1 course. In the Schrödinger picture, the state vectors
describing the system are time independent, their evolution being governed
by Schrödinger equation

1
 d | ψs (t)i
i~ = H | ψs (t) (2)
dt
formal solution of the equation is given in terms of the time evolution operator

| ψs (t)i =Û (t, t0 i | ψs (t0 )i

≡ e−iĤ(t−t0 )/~ | ψs (t0 )i (3)

The operator Û (t, t0 ) is unitary and satisfies the following identities

Û (t, t) = 1
Û † (t, t0 ) = Û (t0 , t) = Û −1 (t, t0 )
Û (t1 , t2 )Û (t2 , t3 ) = Û (t1 , t3 ) (4)

It may be noted that the operators corresponding to the physical observables

are time independent in the Schrödinger picture.
In the Heisenberg picture, on the other hand, the state vectors are time
independent while the operators depend on time. One can therefore, relate
the state vectors of the two pictures by the fact that the Schrödinger state
at time t can be obtained from some initial state at t = 0 by

| ψs (t)i = e−iHt/~ | ψs (0)i ≡| ψH i (5)

where ψH are time independent.

The Heisenberg operators ÂH (t) satisfies the following equation of motion
dAH (t)
i~ = [ÂH , H] (6)
dt
where H is the Hamiltonian of the system, assumed to have no explicit time
dependence. It may be observed that the expectation value of an operator
is the same in both the pictures

hψs (t) | Âs | ψs (t)i = hψh | ÂH (t) | ψH i (7)

where ÂH (t) = eiHt/~ Âs eiHt/~ . Let {| φn i} denote a complete set of eigen-
states of the Hamiltonian H. Consider | ψH i, the Heisenberg state of the
system or equivalently, the Schrödnger state of the system at t = 0 ). We
can write X
| ψH i = cn | φn i (8)
n

2
The coefficients cn are time independent since the left hand side of the above
equation is so. The Schrödinger state at time t can be written as
| ψs (t)i = e−iHt/~ | ψH i
X
= e−iHt/~ cn | φn i
n
X
−iEn t/~
= cn e | φn i (9)
n

Note that the time dependence on the right is contained only in the expo-
nential term e−iEn t/~ , while the coefficient cn are still time independent, a
consequence of the fact that the Hamiltonian has no explicit time depen-
dence.
Suppose now, the Hamiltonian, in addition to the time independent part,
which will henceforth denote by H0 , has a time dependent part V (t)
H = H0 + V (t),
the form of the Schrödinger state at time t, instead of (5) can be written as
X
| ψs (t)i = cn (t)e−iEn t/~ | φn i (10)
n

where the coefficients cn (t) now depend on time. We now define what is
known as interaction picture or Dirac picture which is intermediate between
the two pictures defined above. A state in the interaction picture is defined
by
| ψI (t)i = eiH0 t/~ | ψs (t)i (11)
Note that though at t = 0, the state of the system coincides with that of
Schrödinger picture, the time evolution of the state from t = 0 is governed
by the time-independent Hamiltonian H0 and not by the full Hamiltonian
H, as would be the case for the Schrödinger state. Using the definition (11),
we have
∂ ∂
i~ | ψI (t)i = −H0 eiH0 t/~ | ψs (t)i + eiH0 t/~ (i~) | ψs (t)i
∂t ∂t
iH0 t/~ iH0 t/~
= −H0 e | ψs (t)i + e H | ψs (t)i
= −H0 eiH0 t/~ | ψs (t)i + eiH0 t/~ He−iH0 t/~ eiH0 t/~ | ψs (t)i
= −H0 eiH0 t/~ | ψs (t)i + eiH0 t/~ He−iH0 t/~ | ψI (t)i
≡ VI (t) | ψI (t)i (12)

3
where, we have defined

VI (t) = eiH0 t/~ (H − H0 )e−iH0 t/~ (13)

which is very similar to the way in which Heisenberg operators are connected
to theSchrödinger operators, with H0 replacing H in the time evolution op-
erator.
Clearly, the equation of motion for the operator ÂI (t) in the interaction
picture is given by
dAI (t)
i~ = [ÂI (t), H0 ] (14)
dt
It may be noted that the matrix elements of the operators in both the rep-
resentations (and hence by (7) in all the three pictures) remain the same,

hψs (t) | As | ψs (t)i = hψI (t) | eiH0 t/~ As e−iH0 t/~ | ψI (t)i
= hψI (t) | AI (t) | ψI (t)i (15)

3 First Order Perturbation

We will now obtain a solution of equation (12) governing the time develop-
ment of the wavefunction in the interaction picture,
∂
i~ | ψI (t)i = VI (t) | ψI (t)i
∂t
Let us define time evolution operator by

U (t) | ψI (t = 0)i =| ψ(t)i (16)

The operator U (t) is unitary and we have

∂ ∂
i~ (U (t) | ψI (0)i) = | ψI (t)i
∂t ∂t
= VI (t) | ψI (t)i
= VI (t)U (t) | ψ(t = 0)i (17)

Thus the equation satisfied by the evolution operator is

∂
i~ U (t) = VI (t)U (t) (18)
∂t
4
with U (0) = 1. To first order i perturbation, the solution of the above is

i t
Z
U (t) = 1 − Vi (t0 )dt0 (19)
~ 0
Let us expand | ψI (t)i in terms of the complete eigenstates of the unperturbed
Hamiltonian H0 X
| ψI (t)i = cn (t) | φn i (20)
n

where H0 | φn i = En | φn i. The coefficients cn in (20) are the same as in

(10) corresponding to the Hamiltonian H0 , as can be seen by operating both
sides of the latter by eiH0 t/~ ,
X
eiH0 t/~ | ψs (t)i = cn (t)eiEn t/~ eiH0 t/~ | φn i
n
X
= cn (t) | φn i
n

In terms of these coefficients, (17) can be written as

∂ X X
i~ cn (t) | φn i = VI (t) cm (t) | φm i
∂t n m

Multiplying both sides of above by hφk | and introducing a complete set of

eigenstates, we have
∂ X X
i~ cn (t)hφk | φn i = cm (t)hφk | VI (t) | φl ihφl | φm i
∂t n m,l

Using the orthogonality property of the eigen states, we get

∂ X
i~ ck (t) = cm (t)hφk | VI (t) | φm icm (t) (21)
∂t m

But

hφk | VI (t) | φm i = hφk | eiH0 t/~ V (t)e−iH0 t/~ | φm i

= ei(Ek −Em )t/~ hφk | V (t) | φm i
= Vkm ei(Ek −Em )t/~ ≡ Vkm eiωkm t (22)

5
where
Ek − Em
ωkm = = −ωmk
~
The equation (21) then becomes

∂ X
i~ ck (t) = Vkm eiωkm t cm (t) (23)
∂t m

This equation is still exact but it leads to coupled differential equations for
the coefficients ck (t). We will return to the solution of (23) a little later.
Presently, let us assume that the system is initially in a particular eigenstate
| φn i. Thus cn (t = 0) = 1 and all other coefficients are initially zero. Thus

| ψI (t)i = U (t) | ψI (t = 0)i

= U (t) | φn i
i t
 Z 
= 1− VI (t)dt | φn i (24)
~ 0

The coefficients cm (t) are thus given by

cm (t) = hφm | ψI (t)i (25)

i t
Z
=− hφm | VI (t) | φn idt
~ 0
i t iωmn t
Z
=− e hφm | V (t) | φn i (26)
~ 0

The transition probability from the initial state | φn i to a state | φm i is given

by
Pn→m = |cm |2 (27)

3.1 Constant perturbation

If V does not depend on time but is switched on at time t = 0 for a time t,
one can find out the transition rate easily. Let us designate the initial state

6
by i and the final state by f . The coefficient cf is then given by (26),
Z t
i
cf (t) = − hφf | V | φi i eiωif t/~ dt
~ 0
i eiωif t − 1
= − V if
~ iωif
i 2 sin(ωif t/2)
= − Vif eωif t/2 (28)
~ ωif
The transition probability to the state f is thus given by
4|Vif |2
 
2 2 ωif t
Pi→f = |cf | = 2 2 sin (29)
~ ωif 2
Note that the transition probability depends on (i) the matrix element of the
perturbation between the initial and the final states, and, (ii) thefrequency
difference between the two states, the maximum transition probability oc-
curring when the two states have the same energy, i.e. perturbation neither
extracts energy from the system nor supplies any to it. Taking ωif as a con-
tinuous variable ω, the figure shows the variation of Pi→f as a function of the
frequency difference between the initial state i and the final state f .

4 sin2 (ωt/2)
ω2

t2

ω
−6π/t −4π/t −2π/t 0 2π/t 4π/t 6π/t

Figure 1: Transition Probability as a function of frequency difference between

initial and final states

The figure shows that there is a central peak around ωif = 0 which has a
width of 4π/t and a height of t2 . The widths of the central peak are smaller

7
and height much reduced. Thus appreciable transition from the initial state
takes place to only those final states which lie within |ωif | < 2π/t. This may
be considered as a reflection of the uncertainty principle.
For large time, we have the following representation of the δ function
sin2 (xt)
lim = πδ(x)
t→∞ x2 t
Thus we have
 
2 ωif t
sin
2
lim 2 = πδ(ωif t/2) = 2~πδ(~ωif )
t→∞ ωif t
4
where we have used δ(cx) = (1/|x|)δ(x). Using this, we get, the transition
probability after long enough time to be
2π
Pi→f = t | Vif |2 δ(Ef − Ei ) (30)
~

3.2 Fermi’s Golden Rule

in many situations (for example, in radioactive decay of atoms), there are
many final states possible. In such a case, the transition probability has to
be summed over all possible final states, keeping in mind the requirement
of energy conservation. The probability expression given above (Eqn. (30))
is multiplied by a factor ρf . The reason for the presence of this ”blurring
factor” in Fermi’s Golden rule is the fact that a for transition to take place,
there has to exist states for the system to make a transition to. For instance,
a typical nuclear decay involves release of a quantum γ. Unless there are
states with energy equal to the energy of the initial state minus the energy of
the gamma quantum (see below, discussion on harmonic perturbation), the
decay does not occur.
2π
Pi→f = t | Vif |2 ρf (Ef )δ(Ef − Ei ) (31)
~
where ρf is the density of the final states is defined by ρ(E)dE being the
number of states within an energy interval dE around energy E. Summing
over all possible final states, we get the transition probability to be given by
Z
X 2π 2
Pi → f | Vif | t ρ(Ef )δ(Ei − Ef )dEf
f
~

8
The integration is straightforward because of the delta function and the tran-
sition rate, i.e. probability of transition per unit time to be given by
2π
Wi→f = | Vif |2 ρ(Ei ) (32)
~

3.3 Harmonic Perturbation

Let us consider a perturbation which varies sinusoidally with time. We have
seen that significant transition takes place only when the time dependent
perturbation has a frequency dependence such that the initial and the fi-
nal states are connected by Bohr condition. It is thus desirable to impress
the system with a perturbation having frequency which connects the initial
and final states having energies corresponding to such energy levels. Let us
consider a perturbation
V (t) = V (~r)eiωt (33)
where V (~r) is a hermitian operator, independent of time. In practice, we need
a sine or a cosine function. However,it is convenient to use the exponential
form above and at the end of the calculation we can always take real or the
imaginary part to get appropriate result. The coefficient cf (t) is calculated
in the first order perturbation theory as follows:

i t
Z
cf (t) = − dteiωf i t hφf | V (t | )iφi
~ 0
Z t
i
= − hφf | V (~r) | φi i dtei(ωf i −ω)t
~
0 i(ωf i −ω)t 
i e −1
= − hφf | V (~r) | φi i
~ i(ωf i − ω)
(ωf i − ω)t
 
i sin
= − hφf | V (~r) | φi iei(ωf i −ω)t/2 
 2 
(34)
(ωf i − ω)

~
2
Considering the hermitian conjugate of the perturbation V (t) ∼ eiωt will also
give a similar expression with ω in the above expression being replaced by
−ω. One has to add the two terms and take the square modulus of the sum to
get the transition probability. However, the transition becomes appreciable
only if the resonance condition is satisfied or nearly satisfied, in which case,

9
the trasition probability is given by the square modulus of only one of the
terms. If the final state has a higher energy than the initial state, i.e. if
ωf = ωi + ω, the transition takes place by absorption of radiation from the
perturbing source, whereas, in the reverse case ωf = ωi − ω, the system
emits radiation by a process known as stimulated radiation. For the case of
absorption
2 (ωf i − ω)t
| Vf i |2 sin 2
Pi→f = 2 (35)
~2

ωf i − ω
2
where Vf i = hφf | V (~r) | φi i. The transition probability varies with time with
a period 2π/(ωf i − ω), the peak in the probability occurs when ωf = ωi + ω.
The resonance has a finite width ∆ω = 2π/t so that ∆ωδt = 2π, which is
seen to be a consequence of the uncertainty principle.
To see what happens if the perturbation is switched on for a long time, it
is convenient to assume that the perturbation was switched on at t → −∞.
we take the perturbation to subsist from t = −T /2 to +T /2 and then take
T → ∞ limit. In this case, the calculation of cf (t) gives, changing the
integration limits over time from t = −T /2 to +T /2
Z T /2
i
cf (t) = − Vf i lim ei(ωf i −ω)t dt
~ T →∞ −T /2

i
= − Vf i 2πδ(ωf i − ω)
~
The probability of transition is given by

4π 2
Pi→f = | Vf i |2 δ(ωf i )δ(ωf i ) (36)
~2
The product of two delta functions is handled as follows. We write the rate
of transition
Pi→f
Ri→f = lim
T →∞ T
Z T /2
2π 1
2
= 2 | Vf i | δ(ωf i ) lim ei(ωf i −ω)t dt (37)
~ T T →∞ −T /2

10
Because of the first delta function, we put ωf i = ω in the above integral,
which then evaluates to T and we get
2π 2π
R= 2
| Vf i |2 δ(ωf i − ω) = | Vf i |2 δ(~ωf i − ~ω) (38)
~ ~
The delta function ensures conservation of energy. As discussed earlier, tran-
sition may occur to a host of different final states. The transition rate in that
case is given by Fermi’s Golden Rule
2π
R= | Vf i |2 ρ(Ef − Ei − ~ω)δ(Ef − Ei − ~ω) (39)
~
Fermi’s golden rule can also be derived by assuming that the time dependent
potential is switched on slowly at t → ∞ according to
V (t) = V et e−iωt (wth  > 0)
We look at time scales much smaller than 1/
Z t
i
cf (t) = − Vf i lim ei(ωf i −ω−i) tdt
~ →0 −∞

i ei(ωf i −ω−i)t
= − Vf i lim
~ →0 (ωf i − ω − i)

Thus
1 e2t
| cf |2 = | V f i |2
lim
~2 →0 (ωf i − ω)2 + 2

The transition rate is

d 2e2t 2π
R= | cf (t) |2 = lim 2 2
= 2 | Vf i |2 δ(ωf i − ω) (40)
dt →0 (ωf i − ω) +  ~
which is the same as derived in (39).

4 Two State System

Let us return to the equation of motion (23). We will consider a two state
system with harmonic potential which connects the two states. The unper-
turbed Hamiltonian is
Hu = E1 | 1ih1 | +E2 | 2ih2 | (41)

11
The perturbation term is

V (t) = V e−iωt | 2ih1 | +V ∗ eiωt | 1ih2 | (42)

One can, of course, solve the problem exactly. We will, however, use this
example to demonstrate how the equation of motion works. Suppose, initially
only the lower level, i.e. | 1i is occupied, i.e. c1 (t = 0) = 1 and C2 (t = 0) = 0.
The equation of motion is couples the two states
dc1
i~ = V12 eiω12 t c2
dt
= h1 | V | 2ieiω12 t C2
= V ∗ ei(ω+ω12 )t c2
= V ∗ ei(ω−ω21 )t c2 (43)

Likewise, the equation of motion for c2 is given by

dc2
i~ = V e−i(ω−ω21 )t c1 (44)
dt
One can convert the pair of equations (43) and (44) into a pair of uncoupled
but second order differential equations for c1 and c2 by differentiating each
of the equation once again and substituting from the other equation into it.
For instance, using (44) we have
d 2 c2 dc1
−~2 2
= (i~)(−i)(ω − ω21 )e−i(ω−ω21 )t c1 + V e−i(ω−ω21 )t (i~)
dt dt
dc2
= ~(ω − ω21 )(i~) + | V |2 c2 (45)
dt
where the last line of above is obtained by substituting from (43) and (44).
We therefore have a second order differential equation
d 2 c2 dc2 | V |2
+ i(ω − ω21 ) + c2 = 0 (46)
dt2 dt ~2
We need to solve this equation subject to the initial condition c2 (t = 0) = 0.
Solution is obtained by assuming a solution of the form c2 ∼ eiΩt . Substitut-
ing this form in (46) we get a characteristic equation
| V |2
Ω2 + Ω(ω − ω21 ) − =0
~2
12
which has solutions
r
ω − ω21 (ω − ω21 )2 | V |2
Ω=− ± +
2 4 ~2
The general solution of the differential equation (46) is thus
v v
u 2
| V |2
u 2
| V |2
 
uα uα
 i + t −i + t
t t
c2 (t) = e−iαt/2 Ae 4 ~2 + Be 4 ~2  

where α = ω − ω21 . The condition c2 (t = 0) = 0 gives B = −A, as a result

of which r !
2 2
α | V |
c2 (t) = 2iAe−iαt/2 sin + t
4 ~2
The overall constant A can be fixed by using (44) for time t = 0. This gives

dc2
i~ (t = 0) = V c1 (t = 0)
dt
Differentiating the solution obtained in the previous step for c2 (t) and putting
t = 0 therein
r
dc2 α2 | V |2 V V
i~ (t = 0) = 2iA + 2
= c1 (0) =
dt 4 ~ i~ i~
where we have used c1 (0) = 1. This determines A. Replacing α = ω − ω21 ,
we get the following solution for c2 (t)
r !
2 2
−iV (ω − ω21 ) | V |
c2 (t) = r ei(ω−ω21 )t/2 sin + t
(ω − ω21 )2
|V |2 4 ~2
~ +
4 ~2
The probability of finding the system at the upper level at time t is given
by the square modulus of the above expression
r !
2 2 2
V (ω − ω 21 ) | V |
P2 =| c2 |2 =  2 2
 sin2 + t (47)
2
(ω − ω21 ) | V | 4 ~2
~ +
4 ~2

13
and, of course, the probability of being in the ground state is P1 = 1 − P2 .
Note that the probability of finding the system in the upper level varies with
an angular frequency 2Ω where
r
(ω − ω21 )2 | V |2
Ω= + (48)
4 ~2
When the resonance condition ω = ω21 is satisfied, the amplitude of oscilla-
tion becomes very large. In this situation, at t = 0 (when the system is in the
ground state) the system starts absorbing energy from the time dependent
field, and after a time t = π~/2V = h/4V , it will be found in the excited
state. The system then starts returning energy to the system to return back
to the ground state. The states oscillates with a time period h/2V .
The situation described above has applications to Masers. In ammonia
maser, for instance, there are two eigenstates, the ground state | Si and
the higher state | Ai, the energy difference between the two states lies in
the microwave region. At normal temperatures, the average thermal energy
being much higher than this energy difference (∼ 10−5 eV), the moecules
equally populate these two states. The molecules are separated by passing
them through an inhomogeneous electric field. The molecules in the state
| Ai are then passed through a microwave cavity in such a way that the time
spent by the molecules in the cavity is ∼ h/4V so that when the molecules
emerge from the cavity, they are in the lower state, the energy released has
been absorbed by the field. This is the way we obtain microwave amplifica-
tion by stimulated emission of radiation.

5 Berry Phase
Adiabatic Approximation: In several situations, the Hamiltonian H changed
slowly. When this condition is satisfied, the system has enough time to adopt
to the developing Hamiltonian and the state of the system at a given instant
corresponds to the Hamiltonian at that instant of time. This is in contrast to
Sudden approximation where the system stays in the state of the Hamil-
tonian before change as it is unable to adapt to the sudden change.
In many cases, the Hamiltonian depends on a parameter λ ( or on a set of
parameters, which we collectively denote by λ), where λ(t) is a slowly vary-
ing function of time. For instance, if we consider spins in a slowly varying
magnetic field, λ(t) could correspond to Bx (t), By (t) and Bz (t). In such a

14
situation, we obtain the solution of the Schrödinger equation by adiabatic
approximation. It must be noted that the phrase adiabatic in this context,
unlike in its thermodynamic parlance, has no relationship with the conser-
vation of energy.
A simple example from classical mechanics may illustrate the process.

N
θ

A B

Figure 2: The path of a simple pendulum oscillating in a vertical plane.

Consider an ideal simple pendulum oscillating in a vertical plane. Sup-

posing we start at the north pole N with the plane of oscillation being along
NA (and of course, the local vertical direction at the location of the pendu-
lum. If the movement of the support of the pendulum along NA is sudden,
the resulting motion of the pendulum will be chaotic. However, if the sup-
port is moved slowly, the motion will still remain steady, remaining in the
vertical plane containing the longitude line NA. After reaching the point A,
we move the support parallel to the great circle till the point B and then back
to north pole along BN, thus completing the circuit. However, the plane in
which the pendulum swings is no longer the same (or parallel to) the plane of
oscillation during the outward motion from N, the outbound plane and the

15
incoming plane making an angle θ with one another.This angle is of purely
geometric origin, independent of the shape of the earth and it is equal to the
solid angle subtended by the area NAB at the centre of the latitude circle
along which AB is situated. If R be the radius of this circle, then
A R2 θ
Ω= = =θ
R2 R2
Foucault’s pendulum is also an example of rotation of plane of oscillation,
except that, in that case the support is moved by the earth.
Let us return to quantum mechanics. If the Hamiltonian is time independent,
the evolution of the eigenstate | ψn i with time is given by

| ψn (t)i = e−iEn t/~ | ψn (0)i (49)

where e−iEn t/~ is a purely dynamic phase. We could have multiplied the
same solution by a purely unimportant phase factor eiϕ . However, if the
Hamiltonian is time dependent, we would have
d
i~ | ψn (t)i = H(t) | ψn (t)i = En (t) | ψn (t)i (50)
dt
Here we have assumed that the Hamiltonian varies “slowly” so that En varies
with time but remains an energy eigenvalue. Let us write the solution of
above in a way which reduces to (49) when H does not depend on time. Our
guess for a solution in this case is
i Rt 0 0
− 0 En (t )dt
| ψn (t)i = e ~ | φn (t)i (51)

where
H(t) | φn (t)i = En (t) | φn (t)i
Note that the solution is correct if H is time independent. However, this is
not the whole story because it does not take into account the slow variation
of H(t) itself. To correct for this omission, we take
i Rt 0 0
− 0 En (t )dt
| ψn (t)i = e ~ | φn (t)ieiγn (t) (52)

where the additional factor eiγn (t) must be unity (or eiϕ with ϕ being inde-
pendent of time) if our previous ansatz (50) is correct. Substitute (52) into

16
Schrödinger equation
i Rt iR
∂ | ψn (t)i iγn (t)
− 0
0 En (t )dt
0
∂ | φn (t)i − 0t En (t0 )dt0 iγn (t)
i~ = En | φn (t)ie e ~ + i~ e ~ e
∂t ∂t
i Rt 0 0
− 0 En (t )dt ∂γn (t)
− ~e ~ | φn (t)ieiγn (t)
∂t
= H(t) | ψn (t)i = En (t) | ψn (t)i (53)

This implies that the last two terms on the right had side of the first step of
the above equation equals zero,

∂ | φn (t)i ∂γn
i~ − ~ | φn (t)i =0
∂t ∂t
which gives Z t
∂φn (t)
γn (t) = i dt0 hφn (t) | i (54)
0 ∂t
If we revert back to the parameter λ, which determines the time variation of
H(t), we get
Z λf
∂φn (t)
γn (t) = i dλhφn (λ) | i (55)
λi ∂λ

5.1 Example:
Consider a particle whose spin is aligned in the direction of a magnetic field
~
B(t) which precesses along the z- direction with an angular speed ω, so that
the azimuthal angle ϕ = ωt changes linearly with time.
~ = B[î sin θ cos ωt + ĵ sin ωt + k̂ cos θ]
B

Here θ is the angle of precession which remains constant. The magnetic field
is expressed in energy units by absorbing a factor µ. The Hamiltonian is
given by

H=S ~ = ~σ · B
~ ·B ~
 2 
~B cosθ sin θ cos ωt − i sin θ sin ωt
=
2 sin θ cos ωt + i sin θ sin ωt − cos θ

17
 ~B
which has eigenvalues ± . The spin is initially aligned in the direction of
2
the magnetic field. This is a two state problem of the type developed in the
previous section.

18
 Quantum Mechanics-II
Approximation Methods :
(Semi-Classical Theory of Radiation)
Dipan Kumar Ghosh
UM-DAE Centre for Excellence in Basic Sciences
Kalina, Mumbai
November 21, 2018

1 Introduction
In this lecture we will consider the interaction of electromagnetic radiation
with matter. However, instead of looking at the problem entirely within the
frame of quantum mechanics, which would take us to the subject of quantum
electrodynamics, we use an approach in which the electromagnetic field is
treated as is done in classical electrodynamics, a’ la’ Maxwell’s equations
while matter such are charged particles are treated quantum mechanically,
hence the name semi-classical theory.

2 Interaction of Electromagnetic field with

Charged Particles
The Hamiltonian of a charged particle in an electromagnetic field is obtained
by taking the latter to be described by a scalar potential φ and vector po-
~ Using the expression for the canonical momentum, we write the
tential A.
Hamiltonian as !2
eA~
H = p~ − + eφ + V (1)
c
where V is the potential energy of the particle which binds it to the atom. We
~ to be weak enough to be regarded as perturbation.
take the potentials (φ, A)
The object is to find out what transitions take place between the eigenstate
p2
of the Hamiltonian H0 = + V , the Hamiltonian corresponding to the
2m
system in the absence of the electromagnetic field. The scalar and vector
potentials are not uniquely given but are related by Lorentz gauge condition

1
(Gaussian units)
~ + 1 ∂φ = 0
~ ·A
∇
c ∂t
~ φ which correctly determine the electric and the
Since pair of choice for A,
magnetic fields, the choice of the scalar and vector potentials are not unique.In
empty space, it is always possible to choose φ = 0 as a result of which the vec-
tor potential is now specified in Coulomb gauge in which ∇ ~ · A = 0. We will
now write down the Hamiltonian with choice of gauge. Replacing p~ = −i~∇,
the Hamiltonian is
~2 2 e2 A2 ie~ ~ ~ ie~ ~ ~
H=− ∇ + 2
+ ∇·A+ A·∇
2m 2mc 2mc 2mc
~ · A = 0 because
Note that in the above expression, we cannot directly put ∇
the Hamiltonian operator has to act on a wavefunction to its right. We have
~ · Aψ(~
∇ ~ x) = (∇
~ · A)ψ(~x) + (∇ψ(~
~ x)) · A
~
~ · ∇)ψ(x)
= (A ~

Thus, we get the following for the resulting Hamiltonian

~2 2 ie~ ~ ~
H=− ∇ + V (~r) + A·∇ (2)
2m mc
where we have dropped the term proportional to A2 as the field is taken to
be weak. We take the electromagnetic wave to be an monochromatic x−
polarized wave propagating along the positive z− direction. This is achieved
~ to be given by
by taking the vector potential A
~ x, t) = îA0 cos (kz − ωt)
A(~ (3)

It is easy to check that this expression for vector potential, along with φ0
yields electric and magnetic fields which are mutually perpendicular and the
propagation direction is along the z− direction.
~
~ = − 1 ∂ A = −îA0 ω sin(kz − ωt)
E
c ∂t c
~ =∇
B ~ ×A ~ = −ĵA0 k sin(kz − ωt)

2
Since ω = ck, the fields have the same amplitudes. The intensity is given by
~ × B,
the time average of the Poynting vector (c/4π)E ~ averaged over a period
2π/ω
2
~ = k̂ c A2 ωk hsin2 (kz − ωt)i = ~k c A2 ωk = ω A2 k̂
I = hSi (4)
0 0
4π c 8π c 8πc 0
where we have used the average of sin2 (kz − ωt) equal to 1/2 over a cycle.

3 Dipole Approximation
we will now use time dependent perturbation theory to calculate the prob-
ability of transition between the stationary states of H0 by the last term in
ie~ ~ ~
(2). For a many particle system, this term will be taken as Ai · ∇i =
mi c
P e ~
− i Axi pxi . As discussed in our lectures on time dependent perturba-
mi c
tion theory for harmonic perturbation, we require matrix elements of the
perturbing potential between the stationary states of the unperturbed sys-
tem. Since relevant light wavelengths are of the order of a few hundred
nanometres, where as the size of atoms or molecules is of the order of a few
angstroms at best, we may take the field (and hence the vector potential) to
be constant over the molecular dimensions at a given instant of time. The
approximation so made is called the dipole approximation. We then have
0 ie~ X 1 0 ∂
hψm | V | ψn0 i = Ax hψm (x, t) | | ψn0 (x, t)i
c i
m i ∂x i

ie~ (−i/~)(En −Em )t X 1 0 ∂

= e Ax hψm (x) | | ψn0 (x)i (5)
c i
m i ∂x i

Since the differential operator acts only on the space part of the wavefunction,
the time dependence e−(i/~)(En −Em ) remains unchanged. We need to only
0 ∂
then evaluate the matrix element hψm | | ψn0 i. Let us write down the
∂xi
Schrödinger equation for the wavefunction ψn0 and for the conjugate of ψm 0
,
d2 ψn0 2m
+ 2 (En − V (x))ψn0 = 0 (6a)
dx2 ~
d2 ψm
0∗
2m 0∗
2
+ 2 (Em − V (x))ψm =0 (6b)
dx ~

3
 0∗
Multiply (6a) by xψm and (6b)by xψn0 and subtract, we get
2 0∗ 2 0
2m 0∗ 0 0 d ψm 0∗ d ψn
(En − E m )ψm xψ n = xψ n − xψm
~2 dx2 dx2
We will now simplify the above equation by integrating both sides over x
from −∞ to +∞,
Z ∞ Z ∞ 2 0∗ 2 0

2m 0∗ 0 0 d ψm 0∗ d ψn
(En − Em ) ψm xψn dx = xψn − xψm dx
~2 −∞ −∞ dx2 dx2
0∗ Z ∞ 0∗
0 dψm ∞ dψm d(xψ0n )
= xψn |−∞ −
dx −∞ dx dx
0 Z ∞ 0 0∗
0∗ dψn ∞ dψn d(xψm )
− xψm |−∞ + dx
dx −∞ dx dx
Z ∞ 0∗ Z ∞
dψm d(xψ0n ) dψn0 d(xψm0∗
)
=− dx + dx
−∞ dx dx −∞ dx dx
Z ∞ 0∗ Z ∞
dψm n dψn0 0∗
=− ψ0 dx + ψm dx
−∞ dx −∞ dx

where we have integrated each term on the right hand side by parts. The
first and the third terms of the previous expression were set to zero because
the wavefunctions vanish in the limits. After that we carried out the differ-
entiation explicitly in the third line and cancelled a pair of equal terms. Let
us now carry out an integration by parts of the first term in the last step,
leaving the remaining term unchanged, we get
Z ∞ Z ∞ 0 Z ∞
2m 0∗ 0 0∗ 0 ∞ 0∗ dψn dψn0 0∗
(En −E m ) ψ m xψn dx = −ψ ψ |
m n −∞ + ψm dx+ ψm dx
~2 −∞ −∞ dx −∞ dx

Once again, putting the first term on the right as zero, and observing that
the last two terms are identical, we have
Z ∞ Z ∞
2m 0∗ 0 dψn0 0∗
(E n − Em ) ψm xψn dx = 2 ψm dx (7)
~2 −∞ −∞ dx

Returning to the ket notation, we have

0 d m
hψm | | ψn0 i = 2 (En − Em )hψm
0
| x | ψn0 i (8)
dx ~

4
It is now straight forward to extend it to the case of many particles. Multiply-
ie~ P ie~ ∂
ing both sides of the above equation by and recognizing that i
c c ∂xi
is the perturbation V , we have, on returning back to eqn. (5)

ie~ X 1 ∂
0
hψm (x, t) | V | ψn0 (x, t)i = Ax e(−i/~)(En −Em ) 0
hψm (x) | | ψn0 (x)i
c i
m i ∂x i

i
= Ax e(−i/~)(En −Em )t (En − Em )xmn (9)
c~
where X
0
xmn = hψm |e xi | ψn0 i (10)
i

is the dipole matrix element.

Having established the equivalence of the elements momentum operator
and the dipole matrix elements in this approximation, we will now use the
time dependent perturbation theory to calculate matrix elements of different
transitions in this approximation.

4 Use of time dependent perturbation theory

The equation of motion of the amplitude of the state k was derived earlier
to be given by
dck X
i~ = Vkm eiωkm t cm (t) (11)
dt m

Suppose at t = 0 the system is in a particular state n, i.e. let cn (t = 0) = 1

and the population of all other states be zero. We then have,
dck
i~ = hk | V | niei(Ek −En )t/~ cn (t)
dt
i
= Ax xkn (En − Ek )ei(Ek −En )t/~ (12)
c~
where xkn = hk | ex | ni. Let us consider monochromatic light of angular
frequency ω given by
A0 iωt
e + e−iωt


Ax = A0 cos(ωt) =
2

5
The equation of motion for the state k becomes
dck A0 i(Ek −En +~ω)t/~ i(Ek −En −~ω)t/~


= x kn (E n − E k ) e + e
dt 2c~2
Integrating, we get
 i(Ek −En +~ω)t/~
ei(Ek −En −~ω)t/~

1 e
ck = A0 xkn (En − Ek ) + (13)
2c~ i(Ek − En + ~ω) i(Ek − En − ~ω)

4.1 Rotating Wave Approximation

We will consider various processes which are included in the above solution
(13) of the equation for the population amplitude of the k−th state, using
the so called Rotating Wave approximation in which terms which rapidly
fluctuate in time are neglected on averaging. We first start with the case
where the energy of the k−th state is more than that of the initial n−th state.
This is clearly obtained by absorption of energy from the external agency.
For this to be significant, the energy quantum of the external perturbation
must match with the energy difference between the k−th and the n−th state,
i.e. Ek ' En + ~ω. When this happens, the second term in the expression
(13) becomes small, resulting in the contribution to the population amplitude
from the first term to become negligible. In such a situation we neglect the
first term and obtain for the probability of the population of the k−th state
to be given by the absolute square of the second term od (13),
 
2 Ek − En − ~ω
sin t
2 A20 2 2 2~
| ck | = 2 2 | xkn | (En − Ek ) (14)
c~ (Ek − En − ~ω)2
In this equation ∆E = Ek − En − ~ω gives you the amount by which the
absorption is off the exact resonance condition. Define

A20
C= 2 2
| xkn |2 (En − Ek )2
c~
so that  
2Ek − En − ~ω
sin t
2 2~
| ck | = C (15)
(Ek − En − ~ω)2

6
 sin x t2
Since limx→0 = 1, the maximum value of the above is C 2 which
x 4~
occurs at the place where the resonance condition is exactly satisfied. As
one goes away from the resonance, the height of the curve diminishes fast.
This is consistent with the fact that the maximum probability increases as
the time of exposure of the external radiation increases. The width of the
central peak is 4π~/t.

| ck |2
Ct2 /4~2

∆E
−6π~/t −4π~/t −2π~/t 0 2π~/t 4π~/t 6π~/t
4π~/t

Figure 1: Transition Probability as a function of detuning ∆E between the

initial state n and the final state k

Recalling that as per (4), the expression for intensity is given by

ω2 2
I= A
8πc 0
so that we may rewrite the constant C in the above expression as
8πIx
C= | xkn |2 (En − Ek )2
ω 2 c~2
where we have replaced Ix in place of I in (4) to take care of the fact that
the wave was taken to be x-polarized. The total probability of transition is
R ∞ sin2 x
obtained by integrating over all frequencies ∆E. Since −∞ = π, we
x2

7
have, the total probability of transition to the state k is given by

C ∞ sin2 (∆Et/2~)
Z
Pk = d(∆E)
h −∞ (∆E)2
Ct
= 2 (16)
4~
Thus, as expected the probability is proportional to the duration of exposure
to the incident radiation. Since maximum contribution to the transition
probability comes from the resonant frequency for which ~ω = Ek − En , we
may replace En − Ek by ~ω in the above expression for C and get
8π
C= Ix | xkn |2
c
Using this in the expression for the total probability (16) we get
2π
Pk = 2
Ix | xkn |2 t (17)
c~
Thus the transition probability per unit time in the dipole approximation
is given by
2π
Wn→k = Ix | xkn |2
c~2
where xkn is the matrix element of a dipole oriented along the x-direction,
which was taken as the direction of polarization of the incident radiation.

E2

hν

E1

Figure 2: Stimulated Absorption of radiation

8
 In general, the polarization can be in arbitrary direction. In such a case,
if θ is the angle between the dipole direction and the direction of the polar-
ization of the incident radiation, we may substitute | µkn |2 cos2 θ in place of
| xkn |2 and average over θ. Since average of cos2 θ is 1/3, we have
2π
Wn→k = 2
I | µkn |2 (18)
3c~
One can also express the result in terms of energy density of radiation ρ(νkn )
which is related to the intensity at ν by I = c2 ρ(ν). We then get
2π
Wn → k = | µkn |2 ρ(νkn ) (19)
3~2
We define Einstein B12 coefficient for absorption of isotropic radiation by
2π
B12 ρ(ν12 ) = | µ12 |2 ρ(ν12 ) (20)
3~2
In the presence of radiation field, if the energy of the incident photon hν is
equal to the energy difference E2 −E1 between the initial excited state 2 with
energy E2 and the lower lying, final state 1 with energy E1 , the incoming
photon interacts with the excited electron, causing it to drop to the lower
level. In such a situation, the first term in (13) becomes the dominant term
in the rotating wave approximation. Since the structure of this term is very
similar to the absorption term, we get identical expression for the transition
probability for stimulated emission as we got for the absorption. In this case
we define Einstein B21 coefficient for stimulated emission. and we have

B12 ρ(ν12 ) = B21 ρ(ν12 )

B12 and B21 are thus probability per unit time per unit spectral energy
density, and are measured in J −1 m3 s−2 (in SI).

9
 E2

hν hν
hν

E1

Figure 3: Stimulated Emission of radiation

This process is an important process in generating a large number of

photons which are coherent, as the photon emitted in the process of emission
is coherent with the incident photon. This is used in achieving Laser action.

4.2 Spontaneous Emission - Einstein A coefficient

We have so far considered the process of absorption and stimulated emission,
which gave rise to two of Einstein coefficientsB12 and B21 , which turned out to
have the same magnitude. There is yet another process, viz., spontaneous
emission which does not require presence of external radiation. This occurs
if by some process, the system happens to be in in an excited state 2, with
energy E2 while there exists a lower lying state 1 with energy E1 to which it
can decay without violating other applicable selection rules. The electron in
the excited state will then spontaneously decay to the lower state, releasing
the energy hν = E2 − E1 in the process.

10
 E2 , N2

hν

E1 , N1

Figure 4: Spontaneous Emission of radiation

Suppose there are N2 number of atoms in state 2 and N1 in state 1.

At thermal equilibrium, their population ratios are given by the Boltzmann
factor
N2
= e(E1 −E2 )/kT ≡ e−hν/kT (21)
N1
where E2 − E1 = hν. Further, by definition, the rate of transition from the
state 2 to state 1 must exactly be equal to the rate of transition from the
state 1 to the state 2. Transition from the state 1 to the state 2 occurs only
by absorption of radiation while the reverse transition from the state 2 to
state 1 occurs by both spontaneous and stimulated emission. We, therefore,
have by principle of detailed balance
N2 [A21 + B21 ρ(ν)] = N1 B12 ρ(ν)
where the first tem on the left is the spontaneous emission rate defined by
Einstein’s A coefficient A21 or just A defined as the probability per unit
time of transition from an upper energy state to a lower energy state dy
spontaneous emission of radiation. Using (??) we get
N2 Bρ(ν)
= e−hν/kT =
N1 A + Bρ(ν)
where we have used B12 = B21 = B and used A21 = A. The former relation
need not, in general be true and one could have
B12 g2
=
B21 g1

11
where g1 and g2 are statistical weights of the two levels. Solving the above
for ρ(ν) , we get
A 1
ρ(ν) = hν/kT
(22)
Be −1
which tells us that of the three Einstein coefficients, only one is independent.
The relationship (22) must be true in general, whether or not there exists a
thermal equilibrium, as ρ is a property of external radiation. In particular, it
must also be true for a black body which satisfies Planck’s radiation formula

8πhν 3 1
ρ(ν) = 3 hν/kT
(23)
c e −1
which gives a relationship between A and B coefficients

8πhν 3
A= B (24)
c3
Substituting the expression (20), we get

32π 3 ν 3
A= 3
| µ12 |2 (25)
3c ~
This shows that the rate of spontaneous emission is proportional to the cube
of frequency. This is the reason why it is difficult to construct an X-ray laser
as the X-ray frequency is very high making the spontaneous emission rate
much higher than the stimulated emission rate, as seen by (24). For laser
operation it is necessary that the stimulated emission rate dominate over the
spontaneous emission rate.

12
 Quantum Mechanics - II
Scattering Theory- I
Dipan Kumar Ghosh
Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
November 23, 2019

1 Introduction
Collision processes provide us information about the internal structure of
the target and the forces that come into play during the scattering process.
Historically, scattering of alpha particles by nucleus of gold provided the
first conclusive evidence regarding the structure of nucleus. Diffraction of
low energy electrons and scattering of x-rays is used to determine the charge
distribution inside nuclei.
The effect of collision is usually measured by “cross section” for a particular
process to occur. Physically this means that if a reaction is to occur, the
projectiles must hit an area of the size of the cross section, perpendicular to
the path of the projectiles. The unit of cross section is a “barn” (= 10−24
cm2 ) and it depends on the type of reaction and the energy of the projectiles.
For instance, the nucleus of Boron has a cross section of 120 barns for capture
of fast neutrons with energy of the order of 1 eV but the cross section rises
by ten-fold for capture of thermal neutrons having energy of the order of 25
meV, which accounts for Boron being a good neutron absorber. This cross
section is not to be confused with the physical cross section target atoms,
which in case of Boron is just about 0.1 barn.
In a typical scattering experiment, a beam of projectiles “collide” with the
target particles in its path. All such targets which lie within an area A,
perpendicular to the path of the beam, can interact with the projectile with

1
 2
dA=r d Ω

Incident Beam dΩ Undeflected

Figure 1: Illustrating the basic scattering process

some probability. Those particles in the projectile beam which which do

interact with the target are deflected from their original path while those
which do not continue to move along their original direction.

2 Differential Scattering Cross section

Let F be the incident flux, defined as the number of particles crossing a unit
area perpendicular to the beam direction per unit time, thereby having the
dimension of 1/area-time. The number of particles ∆N scattered into a solid
angle dΩ(θ, ϕ) in time ∆t is proportional to F ∆tdΩ,

dσ(θ, ϕ)
∆N = F ∆tdΩ (1)
dΩ

dσ(θ, ϕ)
The proportionality constant in the above equation is defined as
dΩ
the differential
scattering cross section which is the number of particles scattered into a solid
angle dΩ(θ, ϕ) per unit time per unit incident flux. The total scattering cross
section σ is just the integrated differential scattering cross section over the

2
whole range of the solid angle,
Z
dσ(θ, ϕ)
σ= dΩ
dΩ
Z 2π Z π
dσ(θ, ϕ)
= dϕ sin θdθ (2)
0 0 dΩ
For situations with azimuthal symmetry, which frequently occurs,
Z π
dσ(θ, ϕ)
σ = 2π sin θdθ
0 dΩ
If the flux is time independent, the wave function will be stationary. As
r → ∞, we can write the wave function as a sum of the incident and the
scattered wave functions
u(~r) → uinc + usc
The incident beam actually consists of a wave packet but we will take this
to be a beam of free particles with their wavefunctions being represented by
plane waves. It is convenient to work in the position representation. Strictly
1
speaking, the free particle wave function eikz is not normalizable. We
(2π)3/2
interpret | u |2 as the number of incident particles per unit volume. The flux
is then given by

F =| uinc |2 v
~k
=| uinc |2
m
1 ~k
= (3)
(2π)3 m

We take the scattering to be elastic. Let the direction of the incident particles
be taken along the z-axis. Let the wave function in the scattering region be
written as u = A(eikz + g(~r)). We can write the Schrodinger equaltion
satisfied by the wave function in the scattering region as

~2 d2
   2 
ikz ~ 2
A − −E e +A ∇ − E g(~r) = −V (~r)u(~r)
2m dz 2 2m

3
 Expressing the laplacian in spherical coordinates, we can write this equa-
tion as
 2 2
~2
 2
∂2
     
~k ikz ∂ 2 ∂ 1 ∂ ∂ 1
A − −E e +A − + + sin θ + 2 2 − E g(~r)
2m 2m ∂r2 r ∂r r2 sin θ ∂θ ∂θ r sin θ ∂ϕ2
= −V (~r)g(~r)

At large distances from the scatterer, i.e. as r → ∞, V (~r) → 0. Since the

~2 k 2
scattering is elastic, we must have E = so that the first term on the
2m
left vanishes, and we get the equation satisfied by the scattered wave to be,

~2 2
− ∇ g(~r) = Eg(~r)
2m
We know that the solution of the above equation is separable in radial and
angular coordinates. The solution has the form

eikr
g(r) = f (θ, ϕ)
r
where because of our interest in scattering solution, we have only written
the outgoing wave solution, ignoring the incoming wave. Thus the number
of particles scattered in time dt is given by

∆N = F (∆S)dt
= F (r2 dΩ)dt
~k 2
=| usc |2 r dΩdt
m
~k
=| f (θ, ϕ) |2 dΩdt
m
Comparing the above with (1), we see that the differential scattering cross
section is given by
dσ
=| f (θ, ϕ) |2 (4)
dΩ
The asymptotic form of the wafefunction at large distances from the scatter-
ing centre is given by

eikr
u(r) → eikz + f (θ, ϕ) (5)
r
4
Thus the coefficient of eirk /r gives the scattering amplitude. The equation
satisfied by u is given by

~2 2
− ∇ u(~r) + V (r)u(~r) = Eu(~r)
2m
~2 jk 2
Since the scattering is elastic, we can substitute E = and rewrte the
2m
equation as
2m
(∇2 + k 2 )u(~r) = 2 V (r)u(~r) (6)
~

3 Green’s Function
We will obtain the solution of the differential equation (6). The formal way
of solving equations of such type is by the method of Green’s function.

1. Suppose L is a linear differential operator. The Green’s function is

defined so as to satisfy

L(~x, ∇)G(~x, ~x0 ) = δ 3 (~x − ~x0 ) (7)

where the delta function is a three dimensional delta function.

2. If G0 is a solution of the homogeneous equation LG0 = 0, we can add

G0 to G and the sum will satisfy the Green’s function equation.

3. If G1 and G2 are two solutions of the differential equation (7), G1 − G2

will satisfy the homogeneous equation.

The proof of the last two properties are obvious.

The connection of the Green’s function with the solution of differential
equation is that, given a differential equation Lu(~x) = F (~x), the formal
solution can be written as
Z
u(~x) = u0 (~x) + G(~x, ~x0 )F (~x0 )d3 x0 (8)

where Lu0 = 0 is the homogeneous equation corresponding to the given

differential equation. The proof of (8) is readily obtained by first operating

5
both sides of (8) by L , substituting (7) and observing that F (~x) can be
written as Z
F (~x) = F (~x0 )δ 3 (~x − ~x0 )

[It may be noted that in some sense finding the Green’s function is similar
to finding the inverse of the operator L because if we had a matrix equation
Lu = F the formal solution for u would be given by L−1 F ]

We will now apply this method to solve (6), in which the operator L =
2m
∇2 + k 2 and F (~x) = 2 V (x)u(~x). The corresponding Green’s function
~
satisfyes,
(∇2 + k 2 )G(~x, ~x0 ) = δ 3 (~x − ~x0 ) (9)
Since (∇2 + k 2 ) and δ 3 (~x − ~x0 ) are invariant under translation of coordinates,
the Green’s function is a function of the difference ~x − ~x0 . Thus we express
the Fourier transform of the Green’s function and that of the delta function
as,
Z
0 1 0
G(~x − ~x ) = 3
ei~q·(~x−~x ) G(~q)d3 q (10)
(2π)
Z
0 1 0
δ(~x − ~x ) = 3
ei~q·(~x−~x ) d3 q (11)
(2π)

Inserting (10)and (11) into (9), we get

(−q 2 + k 2 )G(q) = 1

so that
1
G(~q) = (12)
k2 − q2
except at the point q = k, where G(q) diverges. The reason for the divergence
is related to the fact that the homogeneous equation

(∇2 + k 2 )u(~x) = 0

is known to be satisfied by plane waves. Thus the operator ∇2 +k 2 has a zero

eigenvalue. In trying to find the Green’s function, we are trying to invert an
operator having a zero eigenvalue .(Formally, what the Green’s function for
Lu = F attempts to do is to obtain u = L−1 F ) The matrix representation of

6
 Im q

k+i η
Rl q
−k−iη

Figure 2: Poles of the Green’s Function

such an operator clearly has zero determinant whoch precludes its inversion.
Thus we consider a slightly different operator ∇2 + k 2 + i) and will take
 → 0 at the end of the calculation. We than have the following solution for
the Green’s function instead of (12):
1
G(~q) = (13)
k2
− q 2 + i
The coordinate space Green’s function is the inverse Fourier transform of
(13) Z
0 1 0
G(~x − ~x ) = 3
e−i~q·(~x−~x ) G(~q)d3 q (14)
(2π)
In evaluating (14), we first perform the angle integration. The azimuthal
integration gives 2π. Substituting cos θ = µ, we have,
Z ∞ Z 1
0 1 0 1
G(~x − ~x ) = 2 2
q dq dµeiq|~x−~x |µ 2
4π 0 −1 k − q 2 + i
Z ∞ 0
1 1 eiq|~x−~x |
= 2 qdq (15)
4π i | ~x − ~x0 | −∞ k 2 − q 2 + i

where we have subsumed the factor of 2 arising out of the angle integration
by changing the limit of the integration over q. We treat q as a complex
variable which has poles at the roots of k 2 − q 2 + i = 0. We can write
this as q = k ± iη, where 2kη − η 2 = , i.e., η ≈ /2k. The location of the

7
poles are shown in Fig. (2). The integration is now readily performed by
using the residue theorem. Taking the contour in the anticlockwise direction,
the contribution from the semicircular arc can be shown to vanish and the
contour integral is given by 2π times the residue at the included pole at
q = k + iη.Expressing the denominator of the preceding expression as a
partial fraction, the residue is seen to be −1/2 and we get for the coordinate
Green’s function the following expression:
1 
x0 | x0 |

G(~x − ~x0 ) = − − e x−~
ik|~
+ e −ik|~
x−~
(16)
4π | ~x − ~x0 |

Thus there are two solutions G+ and G− which respectively represent the
outgoing and incoming solutions. The scattered waves are only outgoing
solutions, which gives the appropriate Green’s function to be
0
0 eik|~x−~x |
G(~x − ~x ) = − (17)
4π | ~x − ~x0 |

4 Lippmann-Schwinger Equation
Let us take the scatterer to be located at the origin. We assume that the po-
tential describing the scattering centre is short ranged, V (~x) = 0 as x → ∞.
It is reasonable to assume that beyond some typical length scale a associ-
ated with the scatterer, the effect of the scatterer is not felt, so that beyond
this range the scattered particles behave like and obey the free particle wave
equation.
~2 2
− ∇ ψ(~x) = Eψ(~x) (18)
2m
~2 k 2 1 ~
which has eigenvalues and eigenfunctions 3/2
eik·~x . In the Schrödinger
2m (2π)
picture, the time dependent state is simply ψ times an uninteresting phase
2 2
factor ei~ k t/2m . This assumption is actually unphysical, as the incident wave
is a wave packet containing a superposition of plane wave states with a spread
in momentum Z
ψg (t) = d3 kg(k) exp(−i~2 k 2 t/2m)φk

where φk are normalized eigen vectors of the momentum operator with eigen-
value ~k and g(k) is a smooth function of k peaked at some wave number k0 .

8
 R
The normalization of ψg is equivalent to the condition | g(k) |2 d3 k = ~3 .
As the particles approach the scatterer, they experience the effect of the po-
tential. The wave equation that is satisfies in the region where the potential
is non-zero is
~2 2
 
− ∇ + V (~x) ψ(~x) = Eψ(~x) (19)
2m
At large distances x → ∞, it once again behaves like a free particle satisfying
~2 2
− ∇ ψ(~x) = Eψ(~x) (20)
2m
The question that we need to answer is how have the eigenfunctions been
modified in the presence of the potential. In order to answer this, we rewrite
(19) in the ket notation as
(E − H0 ) | ψi = V | ψi (21)
p2
where H0 = is the free particle Hamiltonian. Formally, we may write
2m
the solution of the equation as
1
| ψi = V | ψi (22)
E − H0
1
This, however, causes a singularity problem as is ill defined at its
E − H0
singular point. In order to provide a sense to the operator expression, we
add i to the denominator when we integrate over the eigenvalues of H0
1
| ψi = V | ψi (23)
E − H0 + i
with  > 0+ . The limit  → 0+ will be taken at the end of the calculation.
This is known as the Lippmann-Schwinger equation. This is a solution
only in a formal sense because | ψi appears in both the left and the right of
the equation.
The equation (23) has a formal solution
1
| ψk+ i = φk + V | ψk+ i (24)
E − H0 + i
where φk satisfies the homogeneous equation
(E − H0 ) | φk i = 0 (25)

9
We could have taken the convergence factor to be −i instead of +i and
found another acceptable solution | ψk− i. The special feature of the solution
| ψ + i is that it gives rise to outgoing waves in the scattering region.
To see that (24) is the Green’s function of the problem discussed in the
previous section, let us express the solution in the position representation.
We have
1
hx | ψ ± i = hx | φk i + hx | V | ψk± i (26)
E − H0 ± i
Clearly, hx | φk i is the free particle wave function in the position representa-
tion
1 ~
hx | φk i = eik·~x
(2π)3/2
Let us look at the kernel of the integral equation (24). We have, for the
second term of this equation, on introducing a complete set of position bases
Z Z
1 ± 1
3 0
d x hx | 0 0
| x ihx | V | ψk i = d3 x0 d3 x00 hx | | x0 ihx0 | V | x00 ihx00 | ψk± i
E − H0 ± i E − H0 ± i
Since V is diagonal in the position representation,

hx0 | V | x00 i = V (x0 )δ 3 (~x0 − ~x00 )

Substituting this, we get the kernel to be given by

Z Z
3 0 1 ±
d x hx | | x iV (x )hx | ψk i ≡ d3 x0 G(x, x0 )V (x0 )ψ ± (x0 )
0 0 0
E − H0 ± i
where G(x, x0 ) is the kernel given by
1
G(x, x0 ) = hx | | x0 i
E − H0 ± i
We may find an expression for G(x, x0 ) by introducing a complete set of
unperturbed states φk
Z
1
G(x, x ) = d3 kd3 k 0 hx | φk ihφk |
0
| φk0 ihφk0 | x0 i
E − H0 ± i
Since φk ’s are eigenstates of H0 , we have
1 δ 3 (k − k 0 )
hφk | | φk0 i =
E − H0 ± i ~2 k 2
E− ± i
2m
10
 which gives
Z
0 1 ik0 ·(x−x0 ) 1
G(x, x ) = d3 k 0 e 2 02
(2π)3 ~k
E− ± i
2m
We will now evaluate the above expression for the Green’s function. Writing
~2 k 2
E= , we have
2m
Z
1 ik0 ·(x−x0 ) 1
G(x − x ) = d3 k 0
0
e
(2π) 3 ~k 2 2
~2 k 02
− ± i
2m 2m
Z ik0 ·(x−x0 )
2m 1 3 0 e
= 2 dk 2
~ (2π)3 k − k 02 ± i
Z ∞ Z 1 0
2m 1 02 0 eikµ|x−x |
= 2 2π k dk dµ
~ (2π)3 0 −1 k 2 − k 02 ± i
Z ∞ ik|x−x0 | 0
2m 1 1 0 0e − e−ik|x−x |
= 2 k dk
~ 4π 2 i | x − x0 | 0 k 2 − k 02 ± i
2m
Except for the constant factor of , this is precisely the expression obtained
~2
for the Greens function in (15). (The lower limit of integration is changed
from 0 to −∞ by observing that there is a symmetry of the two terms when
k 0 → −q 0 . ) The integral is evaluated following method of residues as
explained earlier. Hence, the solution of the Lippmann Schwinger equation
of (26) is given by
0
eik|x−x |
Z
1 i~k·~ 2m 3 0
+
ψk (x) = 3/2
e − 2x
dx 0
V (x0 )ψk+ (x0 ) (27)
(2π) ~ 4π | x − x |
The integral in the above expression has contribution only from small x0
because V (x) is short ranged. In the limit of x  x0 , we have
√ √ 0
 
0 2~
x · ~
x
| ~x − ~x |= x2 + x02 − 2~x · ~x0 ' x2 − 2~x · ~x0 = x 1 − 2
' x − x̂ · ~x0
x
where x̂ is a unit vector along ~x. Thus
0
eik|x−x | eikx −ikx̂·~x0
' e
| x − x0 | x

11
which enables us to write (27) in the asymptotic limit as
Z 3 0
1 i~k·~ 2m eikx d x −ikx̂·~x0
+
ψk (x) = 3/2
e − 2x
e V (x0 )ψ + (x0 ) (28)
(2π) ~ x 4π
Comparing this with the form (5), we can write an equivalent form for the
scattering amplitude
Z 3 0
2m d x −ikx̂·~x0
f (θ, ϕ) = − 2 e V (x0 )ψ + (x0 )
~ 4π

5 Scattering Amplitude Determination - The

Born Approximation
Let us return to (26) and consider the case of elastic scattering. The wave-
function u(~x) in the scattering region satisfies
2m
(∇2 + k 2 )u(~x) = V (~x)u(~x) (29)
~2
where the asymptotic form of the wavefunction is given by
~ eikx
u(~x) → eik·~x + f (θ, ϕ) (30)
x
2mE
where f (θ, ϕ) is the scattering amplitude and k 2 = , with E being the
~2
incident energy. The Green’s function for (29) is defined by
(∇2 + k 2 )G(~x, ~x0 ) = δ 3 (~x − ~x0 )
~
We also have the free particle solution φ(~x) = eik·~x satisfying
(∇2 + k 2 )φ(~x) = 0
which also corresponds to the same energy. The solution for u(~x) is then
given by Z
2m
u(~x) = φ(~x) + G(~x, ~x0 ) 2 V (~x0 )u(~x0 )d3 x0
~
0
The solution for G(~x, ~x was found to be given by in (17)
1 h
x0 | x0 |
i
G(~x − ~x0 ) = − e x−~
ik|~
+ e −ik|~
x−~
4π | ~x − ~x0 |

12
Consider the outgoing solution u+ (~x)
Z ik|~x−~x0 |
i~k·~ 1 e 2m
+
u (~x) = e − x
V (~x0 )u+ (~x0 )d3 x0 (31)
4π | ~x − ~x0 | ~2
If α denotes the angle between ~x and ~x0 ,
√
| ~x − ~x0 |= x2 + x02 − 2xx0 cos α

which, for large x and fixed x0 , may be written as

x0
 
| ~x − ~x |= x 1 − cos α ' x − x0 cos α
0
x
so that
1 1
0
'
| ~x − ~x | x
and
k | ~x − ~x0 |' kx − kx0 cos α = kx − ~k 0 · ~x0
where ~k 0 is the wave vector of the scattered beam with | k 0 |=| k |, so that
0
eik|~x−~x | 1 ~0 0
0
' eikx−ik ·~x
| ~x − ~x | x

Thus for large x

eikx
Z
i~k·~ ~0 0 2m
+
u(~x) = e x
− e−ik ·~x 2
V (~x0 )u+ x0 )d3 x0
k (~ (32)
4πx ~
Comparing with with the asymptotic form of u(~x) in (30), we get the
scattering amplitude to be given by
Z
1 ~ 0 0 2m
f (θ, ϕ) = − e−ik ·~r 2 V (~x0 )u+ x0 )d3 x0
k (~ (33)
4π ~

Instead of using the notation f (θ, ϕ), let us use the notation f (~k, ~k 0 ) where, as
before, ~k is the incident wave vector and ~k 0 is the wave vector of the scattered
wave which makes (θ, ϕ) with the direction of ~k, With this notation we write
an iterative solution for (33) by substituting for u+ x0 ), the form (31). We
k (~
have then,

13
 Z
~ ~ 0 1 ~ 0 0 2m ~ 0
f (k, k ) = − e−ik ·~x 2 V (~x0 )eik·~x d3 x0
4π ~
Z x0 −~
ik|~ x00 |
1 x0 2m
−i~k0 ·~ 0 e 2m
+ e V (~
x ) V (x00 )u+ x00 )d3 x0 d3 x00 (34)
k (~
(4π)2 ~2 | ~x0 − ~x00 | ~2

The first term in (34) is

Z
1 ~0 0 2m ~ 0
fB = − e−ik ·~x 2
V (~x0 )eik·~x d3 x0 (35)
4π ~
is just the Fourier transform of V (~x) . This gives the Born scattering
amplitude. The second term in (34) can be simplified by replacing
x0 −~
ik|~ x00 |
e 1 R i~q·(~x0 −~x00 ) d3 q
by its Fourier transform e . Then
4π | ~x0 − ~x00 | (2π)3 q 2 − (k 2 + i)
the second term becomes
d3 q
Z Z
1 −i~k0 ·~
x0 i~ x0
q ·~ 0 3 0 1 00
e e V (~x )d x 2 2
× 3
e−i~q·~x U (~x00 )u+ x00 )d3 x00
k (~
4π q − (k + i) (2π)

Substituting the expression for Born amplitude (35) and also (34) in this
expression. we get, for the second term

d3 q
Z
1
2 2 2
fB (~k 0 , ~q)f (~q, ~k)
2π q − (k + i)

so that (33) becomes

d3 q
Z
1
f (~k 0 , ~k) = fB (~k 0 , ~k) + 2 fB (~k 0 , ~q)f (~q, ~k) (36)
2π q 2 − (k 2 + i)

5.1 Condition of validity of Born Approximation

The integral form given by (32) is an integral equation for the wavefunction
ψk+ (x).
eikx
Z
i~k·~ ~ 0 0 2m
+
ψ(~x) = e − x
e−ik ·~x 2 V (~x0 )ψk+ (~x0 )d3 x0 (37)
4πx ~
Born approximation consists of replacing ψk+ (x0 ) in the integral on the right
~ 0
by the free particle solution φ(~k) = eik·~x . Thus, the condition for validity of

14
the approximation may be stated in terms of the ratio of the difference in
the magnitudes of the difference and the zeroth order term
ψk (~x) − φk (~x)
1
φk (~x)
One o the integrals involved in the above are determined by the region in
which V (x) is significant. The difference appearing in the numerator in the
above is given by
Z ik|~ x0 |
x−~
2m 3 0 e
− dx V (x0 )ψk (~x0 ) (38)
4π~2 | ~x − ~x0 |
Since V (x) is sufficiently localized, the contribution to the above integral
comes primarily from the region within some radial distance x < a. As the
magnitude of φk (~x) is 1, we may state the condition of validity as
Z ik|~ x0 |+i~k·~
x−~ x
m 3 0e
dx V (x0 ) (39)
2π~2 | ~x − ~x0 |
If we take the origin at x = 0, and, write ~x0 − ~x = ~r, we have
Z ikr
m 3 e ~
2
dr eik·~r V (r)  1 (40)
2π~ r
We now have two cases.
(i) Low energies for which ka  1. As the range over which V (r) gives
significant contribution is small, the phase factors nearly remain constant, so
that the condition of validity becomes
Z
m V (r)
2
d3 r 1
2π~ r
Taking the value of V0 in the region everywhere to be its maximum value
V (r) , the left hand side becomes
Z 3
m dr m
V 0 = × 4πa2
2π~2 r 2π~2
so that the condition becomes
~2
V0 
2ma2
15
(ii) High energies for which ka  1. The oscillations of the phase factor
would make the integral even smaller than the previous case and the range
of validity would be further extended. To get a rough estimate in this case
~
let us multiply and divide the expression on the left of (39) by eik·~x . We then
rewrite the integral as follows :
Z ik|~ x0 |
x−~
2m i~k·~x 3 0 e ~ 0

2
e dx 0
e−ik·(~x−~x ) V (x0 )
4π~ | ~x − ~x |
0
The exponential factor inside the integral may be written as eik|~x−~x |(1−cos θ) ,
where θ is the angle between ~k and ~x − ~x0 . and the above expression becomes
Z x−~
ik|~ x0 |(1−cos θ)
2m i~k·~x 3 0e
e dx V (x0 )
4π~2 | ~x − ~x0 |

In the above, | ~x − ~x0 | has the order of magnitude ∼ a, the range over which
V (x0 ) is significant. Thus the exponential factor may be approximated as
eika(1−cos θ) . Since ka is large, the oscillating exponential will cancel rest of
the integrand beyond an approximate √ region given by ka(1 − cos θ) ≤ 1,
which the range of angle δθ . 1/ ka. The integration over θ would give
a factor of 1/ka. This implies that the integral is 1/ka times its value in
the long wavelength case. The condition for validity of Born approximation
becomes
~2 ka
Vmax 
ma2

5.2 Rutherford Scattering

Born amplitude is simply related to the Fourier transform of the scattering
potential. Coulomb potential being a long range potential, which goes to
zero only as 1/x, it is not readily amenable to Fourier transform calculation.
Instead, what one does is to use a screened Coulomb or Yukawa potential,
given by
e−µx
V (r) = −g
x

16
and take µ → 0 at the end of the calculation. For Yukawa potential, the
Born amplitude as calculated as follows, substituting λ = cos θ:
Z −µx
mg 3 e
fB (θ) = d x ei~q·~x
2π~2 x
Z ∞ Z 1
mg 2 e−µx+iqrxλ
= 2π x dx dλ
2π~2 0 −1 x
Z ∞ iqxλ 1
mg e
= 2 r dx
~ 0 iqx −1
∞
mg e(−µ+iq)x e(−µ−iq)x

= 2 −
i~ q −µ + iq −µ − iq 0
2mg 1
= 2 2
~ µ + q2
Now, q 2 = (~kf − ~ki )2 = 2k 2 (1 − cos θ) where kf = ki = k is the magni-
tude of the incident as well as scattered wave vector for elastic scattering.
Substituting these
2mg 1
fB (θ) = 2 2 2
(41)
~ µ + 2k (1 − cos θ)
The differential scattering amplitude is the square of the above expression.
Integrating over the solid angle, we get the total scattering cross section to
be given by
8πm2 g 2 16πm2 g 2
Z Z
dσ 1 1
σ= = 4
d(cos θ) 2 2 2
= 4
dΩ ~ [µ + 2k (1 − cos θ)] ~ µ (µ + 4k 2 )
2 2

(42)
Taking the limit µ → 0 in (41) gives the Rutherford differential scattering
cross section for Coulomb scattering. For this, set g = Ze2 to obtain
mZe2 1
f (θ) = 2 2 2
2~ k sin (θ/2)
Rutherford differential scattering cross section works out to
dσ m2 Z 2 e4
= cosec4 (θ/2) (43)
dΩ 4~4 k 4
Note, however, the total scattering cross section for Rutherford scattering,
obtained by taking µ → 0 in (42) diverges. The reason for this divergence can

17
be related to the fact that the Coulomb potential has infinite range (∼ 1/r)
as a result of which it interacts with all the particles, leading to an infinite
cross section.

5.3 Born Series

Let us return to the Lippmann-Schwinger equation (27),
0
eik|~x−~x |
Z
2m 3 0
ψk (x) = φk (~x) − 2 dx V (x0 )ψk (x0 )
~ 4π | ~x − ~x0 |

where we have suppressed the superscript + and written ψk (x) as the free
particle wavefunction. Using (17), we may re-express this as
 Z
2m
ψk (~x) = φk (~x) + d3 x0 G(~x − ~x0 )V (x0 )ψk (~x0 ) (44)
~2

which may be expressed in a coordinate independent basis as

| ψk i =| φk i + GU | ψk i (45)
2m
where we have redefined the potential term by absorbing te factor in it
~2
2m
U (x) = V (x)
~2
This equation may be solved iteratively.
(i) First Born Approximation :
Replace | ψk i by the zeroth order solution | φk i on the right of (45)

| ψk i =| φk i + GU | φk i (46)

In terms of wavefunctions,
0
eik|~x−~x |
Z
2m
ψk (x) = φk (~x) − 2 d 3 x0 V (x0 )φk (x0 ) (47)
~ 4π | ~x − ~x0 |
The scattering amplitude in this approximation is given by
2m
f (~k, ~k 0 ) = − 2 hφk0 | V | φk i (48)
~
18
(ii) Second Born Approximation :
Replace | ψk i on the right hand side of (45) by (47)

| ψk i =| φk i + GU [| φk i + GU | φk i]
=| φk i + GU | φk i + GU GU | φk i (49)

In expanded form,
0
eik|~x−~x |
Z
2m 3 0
ψk (x) = φk (~x) − 2 dx 0
V (x0 )φk (x0 )+
~ 4π | ~x − ~x |
2 Z 0 0 00 (50)
e x−~x |
ik|~
eik|~x −~x |
 Z
2m 3 0 0 3 00 00
− 2 dx V (x ) d x φk (~x )
~ 4π | ~x − ~x0 | 4π | ~x0 − ~x00 |
0
eik|~x−~x | eikx −i~k0 ·~x0
As before, we may in (50), replace the term by e and
| ~x − ~x0 | x
obtain a formula for the asymptotic behaviour of the term in the second
Born approximation

2m eikx
Z
~0 0
ψk (x) = φk (~x) − 2 d3 x0 eik ·~x V (x0 )φk (x0 )+
~ 4πx
2 ikx Z 0 00 (51)
eik|~x −~x |
 Z
2m e 3 0 i~k0 ·~
x0
− 2 d xe V (x ) d3 x00
0
φk (~x00 )
~ 4πx 4π | ~x0 − ~x00 |

In this way we may obtain what may be termed as the Born series
∞
X
| ψk i =| φk i + GU | φk i + GU GU | φk i + . . . = (GU )n | φk i (52)
n=0

One may represent the above series diagrammatically as follows :

19
 ~k 0 ~k 0

~k 0
~k ~k ~k
+ + + ...

Figure 3: Diagrammatic representation of successive scattering. The red dot

signifies a seat of potential (scatterer)

20
 Quantum Mechanics - II
Scattering Theory- II
Dipan Kumar Ghosh
Centre for Excellence in Basic Sciences
Kalina, Mumbai 400098
November 24, 2018

1 Introduction
In many situations, we have a spherically symmetric potential V (~r) = V (r)
in which case L2 and Lz are good quantum numbers and {E, l.m} ≡ {k, l, m}
form a basis for the positive energy space of the system.
Consider the incoming beam of particles as propagating along the z-axis,
which clearly has azimuthal symmetry. Since the potential is zero in this
region, {k, l, m} also becomes a basis for the free particles, with a further
constraint that the wavefunction is is also independent of m. The general
solution of
~2 2
 
− ∇ + V (r) = Eu (1)
2m
is then written as a product of the spherical harmonics with m = 0 and a
radial function, satisfying
 
00 l(l + 1) 2m 2
ukl − + 2 V (r) − k ukl = 0 (2)
r2 ~
2m
where k 2 = 2 E. For free particles V (r) = 0 but the angular momentum
~
term is still there, and the corresponding wavefunction φkl satisfies
 
00 l(l + 1) 2
φkl − − k φkl = 0 (3)
r2

1
Basically, what we are trying to do here is to express the solution eikz in
spherical polar coordinates. It will be seen that wavefunction can be written
as a sum of its angular momentum components, each component called a
”partial wave”. It will be shown that the effect of the spherical potential is
to provide a phase shift to each of the angular momentum component. This
will be used to determine scattering amplitude defined earlier.

2 Partial Wave analysis of a Plane Wave

Let us write the solution of the equation (3) as consisting of a radial part and
spherical harmonics with m = 0, the latter reflecting azimuthal symmetry of
the incoming plane wave.
∞
X
φ(~r) = Rl (r)Yl0 (θ, ϕ)
l=0

where r
2l + 1
Yl0 (θ, ϕ) = Pl (cos(θ)
4π
The radial equation is solved by charge of variables from r to ρ = kr in terms
of which the equation becomes

d2 Rl 2 dRl l(l + 1)
+ − Rl + Rl = 0 (4)
dρ2 ρ dρ mρ2

The heneral solution of this equation are spherical Bessel functions jl (ρ) and
Neumann functions (also known as spherical Bessel function of second kind)
nl (ρ). The latter functions diverge at the origin, because of which, we only
keep the spherical Bessel functions.

2
 Figure 1: Spherical Bessel functions and Neumann functions
The behaviour of the spherical Bessel functions near the origin and their
asymptotic behaviour are as follows.

ρl
jl (ρ) → , as ρ → 0 (5)
(2l + 1)!!
1 lπ
→ sin(ρ − ), as ρ → ∞ (6)
ρ 2

The solution of (4) is a linear combination of terms with various values of l,

so that X
eikz = eikr cos θ = Al jl (kr)Pl (cos θ) (7)
l

The Legendre functions satisfy orthogonality conditions

Z 1
2δmn
Pm (µ)Pn (µ)dµ =
−1 2n + 1

where µ = cos(θ). We multiply both sides of (7) by Pm (µ) and integrate over

3
µ
Z 1 X Z 2
ikrµ
e Pm (µ)dµ = Al jj (kr) Pl (µ)Pm (µ)dµ
−1 l −1
X 2δml
= Al jj (kr)
l
2l + 1
2Am jm (kr)
=
2m + 1
The left hand side of the above is an integral representation of jl (kr)
(−1)l 1 iyµ
Z
jl (y) = e Pl (µ)dµ
2 −1

which gives
Am = im (2m + 1)
Substituting this provides an expansion of the plane wave in terms of partial
waves of various values of l:
∞
X
ikz
e = il (2l + 1)jj (kr)Pl (cos θ) (8)
l=0

1
Let us return to (2). If V (r) → 0 faster than , we may rewrite the asymp-
r2
totic behaviour of u(~r) as
eikr
 
1 ikz
u(~r) = e + f (θ) (9)
(2π)3/2 r
because we are justified in neglecting V (r) term as compared to the centrifu-
gal term. However, because in this case we are considering the asymptotic
limit of r → 0, we need not be concerned about the behaviour of the solutions
near the origin. As a result, we must now include the Neumann functions as
well in our solutions in this region. The behaviour of the Neumann functions
at large values of its arguments are as follows.
−(2l − 1)!!
nl (ρ) → , as ρ → 0 (10)
ρl+1
1 lπ
→ − cos(ρ − ), as ρ → ∞ (11)
ρ 2

4
Thus

Rl (r) = Al jl (kr) + Bl nl (kr)

Al lπ Bl lπ
→ sin(kr − ) − cos(kr − ) (12)
kr 2 kr 2
The two terms in the above expression may be combined into a single trigono-
metric function by defining

Al = Cl cos δl
Bl = −Cl sin δl

This gives, in the asymptotic limit (as r → ∞)

 
Cl lπ
Rl (r) → sin kr − + δl
kr 2

Note that the above is the asymptotic solution for V (r) 6= 0 except that V (r)
1
goes to zero faster than 2 . Thus the presence of the potential is to produce
r
a phase shift in the wavefunction in the asymptotic region. We compare this
form with the expected behaviour in the asymptotic region, as given by (9),
so that
eikr
 
l 1 lπ 1 lπ
X X
Cl (2l+1)i sin kr − + δl Pl (cos θ) = (2l+1)il sin(kr− )Pl (cos θ)+f (θ)
l
kr 2 l
kr 2 r

where we have redefined the constant Cl with a factor il for convenience.

Expand the sine functions on both sides of the above expression , we get
X Cl (2l + 1)il  
lπ
 
lπ

exp i(kr − + δl ) − exp −i(kr − + δl )) Pl (cos θ) =
l
2ikr 2 2
X (2l + 1)il  
lπ
 
lπ

eikr
exp i(kr − ) − exp −i(kr − )) Pl (cos(θ) + f (θ)
l
2ikr 2 2 r

Equating coefficients of e−ikr on both sides of above, using the fact that
Legendre polynomials of different orders are orthogonal, we get

Cl = eiδl

5
Now compare the coefficients of eikr on both sides, taking care to cancel
il = eilπ/2 with the corresponding factors coming from expansion of the sine
functions, we get
X (2l + 1)
f (θ) = (e2iδl − 1)Pl (cos θ) (13)
l
2ik

The partial wave scattering amplitude is defined as

(e2iδl − 1) eiδl sin δl
fl (θ) = = ≡ fl (k) (14)
2ik k
Thus X
f (θ) = (2l + 1)fl (k)Pl (cos θ)
l
The differential scattering cross section is then given by
dσ X
=| f (θ) |2 = (2l + 1)(2l0 + 1)fl∗ (k)fl0 (k)Pl (cosθ)Pl0 (cos θ) (15)
dθ l,l0

The total scattering cross section is given by

Z
σ= | f (θ) |2 dΩ
Z 1 X
= 2π dµ (2l + 1)(2l0 + 1)fl∗ (k)fl0 (k)Pl (µ)Pl0 (µ)
−1 l,l0

Using orthogonality of the Legendre polynomials

Z 1
2
Pl (µ)Pl0 (µ)dµ = δl,l0
−1 2l + 1
we get
X sin2 (δl )
σ = 4π (2l + 1) (16)
l
k2
where we have substituted from (14) for fl and fl∗ . Thus we can define the
partial wave contribution to the total scattering cross section as
sin2 (δl )
σl = (2l + 1) (17)
k2
P
so that σ = l σl .

6
3 Optical Theorem
We will use the foregoing analysis to relate the total cross section to the
imaginary part of the forward scattering amplitude. This is useful as often
it is easier to calculate the forward scattering amplitude. We have seen that
X (e2iδl − 1)
f (θ) = (2l + 1) Pl (cos θ)
l
2ik

Thus ∞
1 X
Imf (θ) = (2l + 1)(1 − cos(2δl ))Pl (cos θ)
2k l=0
Then the imaginary part of the forward scattering amplitude is given by
1 X 1X
Imf (0) = (2l + 1)(1 − cos(2δl )) = (2l + 1) sin2 δl
2k l k l

It then follows, using (16)

4π X 4π
σ= 2
(2l + 1) sin2 δl = Imf (0) (18)
k l k

Maximum scattering takes place for δl = π/2.

3.1 Example - Hard Sphere Scattering

As an illustration of the method of partial waves let us consider scattering
of low energy particles from a hard sphere of radius a where
(
0 for r > a
V (r) =
∞ for r < a

Since the potential is infinite for r < a, the wavefunction R(r) = 0 at r = a.

Outside the sphere, the potential being zero, the free particle solution is valid.
Hence
Rl (r) = Al jl (kr) + Bl nl (kr)
Boundary condition at r = a gives Al jl (ka) + Bl nl (ka) = 0 which gives
Al nl (ka)
=−
Bl jl (ka)

7
Let us look at the asymptotic limit of the solution. We have seen that the
solution has the form

   
Cl lπ Cl lπ lπ
Rl (r) = sin kr − + δl = sin(kr − ) cos δ + cos(kr − ) sin δ
kr 2 kr 2 2
(19)
However, the asymptotic limits of Bessel function and the Neumann function
allows us to write the solution in this limit as
   
Al lπ Bl lπ
Rl (r) = sin kr − + δl − cos kr − + δl (20)
kr 2 kr 2

Comparing equations (19) and (20) we get Al = Cl cos δl and Bl = −C sin δl .

Hence
Bl jl (ka)
tan δl = − =
Al nl (ka)
Thus the partial wave scattering cross section is given from (17)

4π 2 4π jl (ka)2
σl = 2 (2l + 1) sin δl = 2 (2l + 1)
k k jl (ka)2 + nl (ka)2

For small ka, only s-wave contributes and we may use the behaviour of jl
and nl near the origin
sin(ka)
j0 =
ka
cos(ka)
n0 = −
ka
which gives
4π
σ = 2 sin2 (ka) ' 4πa2
k
Note that the hard sphere scattering cross section is 4 times the classical
scattering cross section of πa2 .