Modern Quantum Mechanics

Shuai Ouyang1

2021.09.30

1
[email protected]
2
Contents

1 Fundamental Concepts 5
1.1 Stern-Gerlach Experiment and Spin . . . . . . . . . . . . . . . . 5
1.2 Compatible Observables and Uncertainty Relation . . . . . . . . 7
1.3 Unitary Transformation . . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Position, Momentum and Translation . . . . . . . . . . . . . . . . 10

2 Quantum Dynamics 13
2.1 Time Evaluation and Schrodigner Equation . . . . . . . . . . . . 13
2.2 Schrodinger Picture and Heisenberg Picutre . . . . . . . . . . . . 14
2.3 Simple Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . 15
2.4 Schrodinger’s Wave Equation . . . . . . . . . . . . . . . . . . . . 17
2.5 Propagators and Feynman Path Integrals . . . . . . . . . . . . . 18
2.5.1 Feynman Path Integrals . . . . . . . . . . . . . . . . . . . 19

3 Theory of Angular Momentum 21

3.1 Rotations and Angular Momentum . . . . . . . . . . . . . . . . . 21
3.2 Spin 1/2 Systems and Finite Rotations . . . . . . . . . . . . . . . 22
3.3 SO(3), SU(2) and Euler Rotations . . . . . . . . . . . . . . . . . 25
3.3.1 Euler Rotations . . . . . . . . . . . . . . . . . . . . . . . . 25
3.4 Density Operators and Pure Versus Mixed Ensembles . . . . . . 26
3.4.1 Time Evaluation of Ensembles . . . . . . . . . . . . . . . 26
3.5 Eigenvalues and Eigenstates of Angular Momentum . . . . . . . 28
3.5.1 Representation of Rotation . . . . . . . . . . . . . . . . . 29
3.6 Orbital Angular Momentum . . . . . . . . . . . . . . . . . . . . . 30
3.7 Schrodinger’s Equation for Central Potentials . . . . . . . . . . . 32
3.8 Addition of Angular Momenta . . . . . . . . . . . . . . . . . . . . 33
3.8.1 CG Coefficients and Rotation Matrices . . . . . . . . . . . 34
3.9 Tensor Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

4 Symmetry in Quantum Mechanics 37

4.1 Parity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.2 Time Reversal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

3
4 CONTENTS

5 Approximation Methods 39
5.1 Time-Independent Perturbation Theory . . . . . . . . . . . . . . 39
5.1.1 Nondegenerate Case . . . . . . . . . . . . . . . . . . . . . 39
5.1.2 Degenerate Case . . . . . . . . . . . . . . . . . . . . . . . 40
5.2 Time-Dependent Perturbation Theory . . . . . . . . . . . . . . . 42
5.2.1 Interaction Picture . . . . . . . . . . . . . . . . . . . . . . 42
5.3 Variational Mothods . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.4 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.4.1 Quadratic Stark Effect . . . . . . . . . . . . . . . . . . . . 44
5.4.2 Linear Stark Effect . . . . . . . . . . . . . . . . . . . . . . 44
5.4.3 Relativistic Correction . . . . . . . . . . . . . . . . . . . . 44
5.4.4 Spin-Orbit Interaction . . . . . . . . . . . . . . . . . . . . 45
5.4.5 Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . 45
5.4.6 Time-Dependent Pertubation . . . . . . . . . . . . . . . . 45

6 Scattering Theory 47
6.1 Scattering as A Time-Dependent Perturbation . . . . . . . . . . 47
6.2 Partial Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chapter 1

Fundamental Concepts

1.1 Stern-Gerlach Experiment and Spin

The Stern-Gerlach experiment is the first experiment that find the spin of par-
ticle. The details of this experiment we don’t mention again, but we use this
experiment to derive the Pauli matrices. Firstly, the spin-up and spin-down can
be written as: ( ) ( )
1 0
|+⟩ = , |−⟩ = . (1.1)
0 1
We set up an inharmonic magnetic field in z-direction, we can get two spots
with electron. Therefore the spin operator in z-direction Sz satisfies:

ℏ ℏ
Sz |+⟩ = |+⟩, Sz |−⟩ = − |−⟩. (1.2)
2 2
we can calculate the matrix form of Sz with the above equation,
( )
ℏ ℏ 1 0
Sz = [|+⟩⟨+| + |−⟩⟨−|] = . (1.3)
2 2 0 −1

Secondly, we let the spin-up or spin-down beam which goes through the z-
direction inharmonic magnetic field passes through the x-direction and y-direction
megnetic field. We find that the beam is spilited into two beams in both of these
two situations. We can write down the equations of Sx , Sy according the exper-
iments:
1 1
Sx |±⟩ = ± √ |+⟩ + √ |−⟩, (1.4)
2 2
1 i
Sy |±⟩ = √ |+⟩ ± √ |−⟩, (1.5)
2 2
where we using i means the x-direction and y-direction are in different dimen-
sion. We can also derive the matrix form of these two operator from above

5
6 CHAPTER 1. FUNDAMENTAL CONCEPTS

equations:
( )
ℏ ℏ 0 1
Sx = [|+⟩⟨−| + |−⟩⟨+|] = , (1.6)
2 2 1 0
( )
ℏ ℏ 0 −i
Sy = [−i|+⟩⟨−| + i|−⟩⟨+|] = . (1.7)
2 2 i 0

We can calculate the commutator and anticommutator of spin:

ℏ2
[Si , Sj ] = iℏεijk Sk , {Si , Sj } = δij . (1.8)
2
As we can see that three directions of spin operator are relate to three matrices,
which is called Pauli matrix:
( ) ( ) ( )
0 1 0 −i 1 0
σx = , σy = , σz = . (1.9)
1 0 i 0 0 −1

We present the properties of Pauli matrix:



 [σi , σj ] = 2iεijk σk ; (1.10a)
{σi , σj } = 2δij ; (1.10b)

 2
σi = 1. (1.10c)
And we can also write down the ladder operator
( ) ( )
0 1 0 0
S+ = ℏ|+⟩⟨−| = ℏ , S− = ℏ|−⟩⟨+| = ℏ , (1.11)
0 0 1 0

and it’s easy to see that

S± = Sx ± iSy , (1.12)
and it’s commutator and anti-commutator are

[S+ , S− ] = i[Sy , Sx ] − i[Sx , Sy ] = 2ℏSk , (1.13)

{S+ , S− } = i{Sy , Sx } − {Sx , Sy } = 0. (1.14)

We can also calculate the total spin S 2

3 2
S 2 = Si2 = S+ S− + Sz2 = ℏ , (1.15)
4
and can easily prove
[S 2 , Si ] = 0 (1.16)
1.2. COMPATIBLE OBSERVABLES AND UNCERTAINTY RELATION 7

1.2 Compatible Observables and Uncertainty Re-

lation
If the commutator bewteen two operators are zero, we say these two opertator
are compatible. We will study the eigenvalue of compatible operators and in-
compatible operators first, and then prove the uncertainty relation. For given
two operators A, B, if they are compatible and the eigenvalues of A are nonde-
generate, then we can prove the matrix ⟨a′′ |B|a′ ⟩ is diagonal matrix:

⟨a′′ |[A, B]|a′ ⟩ = (a′′ − a′ )⟨a′′ |B|a′ ⟩ = 0,

because the eigenvalues are different, ⟨a′′ |B|a′ ⟩ must be zero, meaning this ma-
trix is diagnoal. Then, let’s we calculate the eigenvalue of B with the help of
above theorem:
∑ ∑
B= |a′′ ⟩⟨a′′ |B|a′′ ⟩⟨a′′ | ⇒ B|a′ ⟩ = |a′′ ⟩⟨a′′ |B|a′′ ⟩δa′′ a′ = ⟨a′ |B|a′ ⟩|a′ ⟩,
(1.17)
the eigenvalue of B is b′ = ⟨a′ |B|a′ ⟩. For degeneracy situations, we can use
Schimidt method to orthogonalize the n-fold sates. The Schimidt method is:
given a set of vectors which are not all orthogonal, we can generate a new set
of vectors which are orhtogonal in the following way:

|b1 ⟩ = |a1 ⟩;
⟨b1 , a2 ⟩
|b2 ⟩ = |a2 ⟩ − |b1 ⟩;
⟨b1 , b1 ⟩ (1.18)
⟨b1 , ai ⟩ ⟨bi−1 , ai ⟩
|bi ⟩ = |ai ⟩ − |b1 ⟩ − · · · − |bi−1 ⟩.
⟨b1 , b1 ⟩ ⟨bi−1 , bi−1 ⟩

Then we will prove several theorems for proving uncertainty relation:

Schwarz inequality: ⟨α|α⟩⟨β|β⟩ ≥ |⟨α|β⟩|2
Proof: We chose a state consisited by |α⟩, |β⟩

|γ⟩ = |α⟩ + λ|β⟩, (1.19)

where λ is a paramater, we use the fact ⟨γ|γ⟩ ≥ 0 to prove Schwarz inequality,

(⟨α| + λ∗ ⟨β|)(|α⟩ + λ|β⟩) = ⟨α|α⟩ + λ∗ ⟨β|α⟩ + λ⟨α|β⟩ + |λ|2 ⟨β|β⟩,

we let λ = − ⟨β|α⟩
⟨β|β⟩ ,

|⟨α|β⟩|2 |⟨α|β⟩|2
· · · = ⟨α|α⟩ − 2 + ≥ 0 ⇒ ⟨α|α⟩⟨β|β⟩ ≥ |⟨α|β⟩|2
⟨β|β⟩ ⟨β|β⟩

We firstly define a new operator

△A := A − ⟨A⟩, (1.20)
8 CHAPTER 1. FUNDAMENTAL CONCEPTS

and its dispersion is

2
σA = ⟨(△A)2 ⟩ = ⟨A2 ⟩ − ⟨A⟩2 . (1.21)
We can easily prove the uncertainty relation with Schwaz inequality:

(σA )2 (σB )2
= ⟨△Aα|△Aα⟩⟨△Bα|△Bα⟩ ≥ ⟨△Aα|△Bα⟩2 ≥ Im(⟨△Aα|△Bα⟩)2
[ ]2 [ ]2
1 1
= (⟨△Aα|△Bα⟩ − ⟨△B|△A⟩) = ⟨α| [A − ⟨A⟩, B − ⟨B⟩] |α⟩ .
2i 2i
[ ]2
1
= ⟨[A, B]⟩
2i
1.3. UNITARY TRANSFORMATION 9

1.3 Unitary Transformation

For two given sets of bases|b⟩, |a⟩, they can be connected by an unitray operator
U . This unitary operator must satisfy U † U = U U † = 1, therefore this operator
can be written as ∑
U= |b⟩⟨a|, (1.22)
we set |b⟩ = U |a⟩. Now, if we have a state that can be expanded by old basis
|a⟩ ∑
|α⟩ = |a⟩⟨a|α⟩,
we want to know the relation between new expandsion coefficients and old co-
efficients. It’s simple to do this:
∑ ∑
⟨bk |α⟩ = ⟨bk |al ⟩⟨al |α⟩ = ⟨ak |U † |al ⟩⟨al |α⟩, (1.23)

it’s clear that |b⟩ = U † |a⟩. We can use the same method in transforming oper-
ator: ∑
⟨bk |X|bl ⟩ = ⟨ak |U † |a′m ⟩⟨a′m |X|a′′n ⟩⟨a′′n |U |al ⟩, (1.24)

and it’s also clear that X ′ = U † XU . Although there are many presentations,
but there still are something be independent to presentations. Trace is one of
this kinds of something, its defination is
∑
tr(X) = ⟨a′ |X|a′ ⟩. (1.25)

It’s easy to prove it is independent to presentation:

∑ ∑ ∑ ∑
⟨a′ |X|a′ ⟩ = ⟨a′ |b⟩⟨b|X|b′ ⟩⟨b′ |a′ ⟩ = ⟨b′ |b⟩⟨b|X|b′ ⟩ = ⟨b|X|b⟩.
(1.26)
In the last of this section, we talk about the uniatry equivalent observables.
What that means? It’s said that for any given two operator A, B, if they can
be connected by an unitary operators in the form of B = U AU −1 , we said B
is unitary equivalent to A. We can prove that the unitary equivalent operators
has the same eigenvalue, but we don’t want to prove this theorem, leaving it for
readers as an expamle.
10 CHAPTER 1. FUNDAMENTAL CONCEPTS

1.4 Position, Momentum and Translation

We deal with the seperate states in the previous section, and now we will deal
with continuous states. The properties of continuous states are similar to prop-
erties of sperate system, don’t be showed in there. We set the eingeinket of
opsition operator is complete, and different components of position operator are
commutative
[xi , xj ] = 0. (1.27)
Now suppose we have a eingeinket located at x′ , and we take a infinitesimal
translation J (dx) : x → x + dx. It’s an operator, and it has the following
properties:


 J (dx)† J = 1; (1.28a)


 J (dx′ )J (dx) = J (dx′ + dx); (1.28b)

 J −1 (dx) = J (−dx′ ); (1.28c)


 lim J (dx) = 0, (1.28d)
dx→0

and it’s easy to prove that this expression meets all the properties
p · dx
J (dx) = 1 − i . (1.29)
ℏ
Let’s see relationship between the position operator and translation operator:
[x, J (dx′ )]|x′ ⟩ = x|x′ + dx′ ⟩ − x′ J (dx)|x′ ⟩ = (x′ + dx′ − x′ )|x′ + dx′ ⟩ ≈ dx′ |x′ ⟩,
(1.30)
take the (1.29) in it, we can get
xp · dx′ p · dx′ x [p, x] · dx′
−i +i =i = dx′ ⇒ [xi , pj ] = iℏδij . (1.31)
ℏ ℏ ℏ
We have mentioned that J is an operator of translation, but it has the momen-
tum operator p in it, meaning the momentum is the generator of translation
under the Noether’s theorem. We have talked about the infinitesimal transla-
tion, but we offten meet the continuous transilation. Forturenally, we can use
(1.28b) to do this:
( )N
ipx △x px △x
J (△xx̂) = lim 1 − = e−i ℏ . (1.32)
N →0 ℏ
Because the different translations are independent, the commutators between
different generators are zero
[J (△xi x̂i ), J (△xj x̂j )] = 0 ⇒ [pi , pj ] = 0. (1.33)
We have studied the properties of momentum operator, now, we will study
the wavefunction expaned in momentum space and position space. Firstly, the
eigenstate of position operator is
x|x′ ⟩ = x′ |x′ ⟩, (1.34)
1.4. POSITION, MOMENTUM AND TRANSLATION 11

and this space is continuous, the inner prodect of different eigenstates is

⟨x′′ |x′ ⟩ = δ(x′′ − x′ ). (1.35)

Then, we can expand the state with bases of position space

⟨x′ |α⟩ = ψα (x′ ), (1.36)

where ψ is the wavefunction we called. And inner product of different states is

∫ ∫
⟨β|α⟩ = dx′ ⟨β|x′ ⟩⟨x′ |α⟩ = dx′ ψβ∗ ψα . (1.37)

The eigenstates also have wavefunction, we can also construct the wavefunction
of state with eigenwavefucntion
∫ ∫
⟨x |α = ψα = dx ⟨x |a ⟩⟨a |α⟩ = dx′ ca′ ua′ ,
′ ′ ′ ′ ′
(1.38)

where ua′ = ⟨x′ |a′ ⟩ is the wavefunction of eigenstate. Next, let’s see the mo-
mentum operator in position space
( )
ip△x′
1− |α⟩
ℏ
∫ ∫
= dx′ J (△x′ )|x′ ⟩⟨x′ |α⟩ = dx′ |x′ + △x′ ⟩⟨x′ |α⟩
∫ ∫ (1.39)
′ ′ ′ ′ ′ ′ ′ ′ ∂ ′
= dx |x ⟩⟨x − △x |α⟩ ≈ dx |x ⟩(⟨x |α⟩ − △x ⟨x |α⟩)
∂x′
∂
⇒ p|α⟩ = −iℏ ′ ⟨x′ |α⟩,
∂x
this equation is very useful, we can let |α⟩ = |x′′ ⟩, get

∂
⟨x′ |p|x′′ ⟩ = −iℏ δ(x′ − x′′ ), (1.40)
∂x′
∂
⟨x′ |p|p′ ⟩ = −iℏp′ ⟨x′ |p′ ⟩ = −iℏ ℏ⟨x′ |p′ ⟩, (1.41)
∂x′
we can slove (1.41)
ip·x
⟨x′ |p′ ⟩ = (2πℏ)−3/2 e ℏ , (1.42)
This is the wavefunction of momentum in position space. Next, we shortly
introduce the wavefunction of state in momentum space and relation of two
kinds of wavefunctions.
∫ ∫
ip·x
ϕp′ = ⟨p′ |α⟩ = dx′ ⟨p′ |x′ ⟩⟨x′ |α⟩ = dx′ (2πℏ)−3/2 e− ℏ ψα (x′ ), (1.43)

this is Fourier transformation we learned before.

12 CHAPTER 1. FUNDAMENTAL CONCEPTS
Chapter 2

Quantum Dynamics

2.1 Time Evaluation and Schrodigner Equation

Time in quantum mechnics is only a paramater not the operator, that is what
we need to remember. But, we can create an operator about evaluation of state
U , its properties are same to properties of operator of translation. Then, we
can write it as
H
U (dt) ≡ 1 − i dt, (2.1)
ℏ
and its dynamic equation is
∂ H ∂
U (t + dt) − U (t) = U dt = −i U dt, ⇒ iℏ U = HU . (2.2)
∂t ℏ ∂t
When it acts on state, the Schrodinger equation comes out. If the evaluation
operator is independent of time, it can be
iH(t−t0 )
U = e− ℏ . (2.3)

If an operator in commutative to evaluation operator, we can write down the

metrix of evaluation operator
∑ ∑ iE ′ t
e− |a′ ⟩⟨a′ |e− |a′′ ⟩⟨a′′ | = |a′ ⟩e− ⟨a′ |,
iHt iHt a
ℏ = ℏ ℏ (2.4)

where we let t0 = 0 for convinence, and the cooefficients are

iE ′ t
ca′ (t) = ca′ (t = 0)e−
a
ℏ . (2.5)

In the last of this section, we simply introduce the correlation amplitude: the
relationship between innitial state and evaluated state, which is

C(t) ≡ ⟨α|U (t, 0)|α⟩. (2.6)

13
14 CHAPTER 2. QUANTUM DYNAMICS

2.2 Schrodinger Picture and Heisenberg Picutre

In the previous sections, the state will evalute with time and the operator won’t
change, this is what we called Schrodinger picture. Now, we will study another
picture——Heisenberg picture, the ket dones’t change but operator evaluates
with time. We use superscript H, S represent the operators in Heisenberg picture
and Schrodinger picture,
AH = U † (t)AS U (t). (2.7)
Firstly, we need to figure out the dynamic equation of Heisenber operator

dAH ∂U† S ∂U 1 1
= A U + U † AS = − U † HAS U + U † AS HU
dt ∂t ∂t iℏ iℏ (2.8)
1 † † S 1 † S † 1 H
= − U HUU A U + U A UU HU = [A , H],
ℏ iℏ iℏ
this is the equation of operator in Heisenberg picture, similar to Poisson bracket.
Next, we will prove Ehrenfest theorem, the quantum mechanics version of
second Newton’s law. Considering a particle move in potential V (x), its Hamil-
tonian is
p2
H= + V (x), (2.9)
2m
we can use (2.8) to get the equation of positon and momentum

dpi 1 ∂
= [pi , V (x)] = − V (x), (2.10)
dt iℏ ∂xi
dxi 1 p2 pi
= [xi , ]= , (2.11)
dt iℏ 2m m
we can get the differential equaiton of position and then get Erenfest thorem

d2 xi ∂2 d2
2
= − 2 V (x), ⇒ m 2 ⟨x⟩ = −⟨∇2 V (x)⟩. (2.12)
dt ∂xi dt

We have said that the state don’t change in Heisenberg picture, but there are
something different between eigenstate in two picture. First, we set the eigenket
in Schrodinger picutre is
A|a′ ⟩ = a′ |a′ ⟩, (2.13)
and we multiply unitary operator to find the eigenequation in Heisenberg picture

U † AUU † |a′ ⟩ = AH (U|a′ ⟩) = a′ U † |a′ ⟩, (2.14)

it’s clear that the eigenket in Heisenberg picture is different compared to in

Schrodinger picture. And it’s interesting that the eigenket in Heisernberg pic-
ture evaluate in opposite path compared to in Schrodinger picture.
2.3. SIMPLE HARMONIC OSCILLATOR 15

2.3 Simple Harmonic Oscillator

We will pass though this section much more quickly, because we have learned
many times. The Hamiltonian of harmonic oscillator is
p2 mω 2 x2
H= + , (2.15)
2m 2
to study it better, we define two ladder operators,
√ ( ) √ ( )
mω ip † mω ip
a≡ x+ , a ≡ x− . (2.16)
2ℏ mω 2ℏ mω
Their commutator is
[a, a† ] = 1, (2.17)
and we define the number operator
N ≡ a† a ⇒ [N, a] = −a, [N, a† ] = a† , (2.18)
therefore the Hamiltonian can be written as
1
H = a† a + . (2.19)
2
We note the eigenket as |n⟩, and we can show that a is annhilation operator, a†
is generation operator, their eigenequations are
√ √
a|n⟩ = n|n − 1⟩, a† |n⟩ = n + 1|n + 1⟩, (2.20)
we can show these two equations with the help of number operator. We note
the ground state as |0⟩ and we can generate |n⟩ with generation operator,
(a† )n
|n⟩ = √ |0⟩, (2.21)
n!
where the eigeneneegy is ( )
1
En = n+ ℏω. (2.22)
2
Next, the martices of these two operators are
√ √
⟨n′ |a|n⟩ = nδn′ ,n ⟨n′ |a† |n⟩ = n + 1δn′ ,n+1 . (2.23)
Besides, we can express position and momentum operators with ladder operators
and obtain the martices of x and p operators:
√ √
ℏ † mℏω
x= (a + a ), p = i (−a + a† ), (2.24)
2mω 2
√
ℏ √ √
⟨n′ |x|n⟩ = ( nδn′ ,n−1 + n + 1δn′ ,n+1 ), (2.25)
2mω
√
′ mℏω √ √
⟨n |p|n⟩ = i (− nδn′ ,n−1 + n + 1δn′ ,n+1 ). (2.26)
2
16 CHAPTER 2. QUANTUM DYNAMICS

We have talked about how to get |n⟩ with ground state, but we haven’t known
what does the eigenfunction of ground state look like. Now, we can get this
equation in position space
√ ( )
′ mω ′ ip ′ 2 d
⟨x |a|0⟩ = ⟨x |x + |0⟩ = x + x0 ⟨x′ |0⟩ = 0, (2.27)
2ℏ mω dx

where √
ℏ
x0 ≡ . (2.28)
mω
The solotion of this differential equation is
( ) ( ′ )2
′ 1 − 21 xx
⟨x |0⟩ = √ e 0 . (2.29)
π 1/4 x0

We have talked about the eigenstate, next, we will talk about the time evaluation
of oscillators. For convience, we use Heisenberg picture, the equations of position
and momentum are
dp 1
= = −mω 2 x, (2.30)
dt iℏ
dx 1 p
= = . (2.31)
dt iℏ m
This pair is coupled, a little different to calculate. But equations of ladder
operators are simple

da 1 da† 1
= [a, H] = −iωa, = [a† , H] = iωa† , (2.32)
dt iℏ dt iℏ
whose solutions are

a(t) = a(0)e−iωt , a† (t) = a† (0)eiωt . (2.33)

Then we can use (2.24) write down x and p:

√
mω p(0)
x(t) = (a + a† ) = x(0) cos ωt + sin ωt, (2.34)
2ℏ mω
√
mℏω
p(t) = i (−a + a† ) = −mωx(0)ω sin ωt + p(0) cos ωt. (2.35)
2
2.4. SCHRODINGER’S WAVE EQUATION 17

2.4 Schrodinger’s Wave Equation

The Schrodinger’e equation is

iℏ∂t ψ = Hψ, (2.36)

and the consevation equation is

∂ρ
+ ∇ · ⃗j = 0, (2.37)
∂t
where
⃗j = − iℏ (ψ ∗ ∇ψ − ψ∇ψ ∗ ). (2.38)
2m
And we can rewrite the conservation equation, to make it looks like fluid
∂ρ
+ ∇ · (ρ⃗v ) = 0, (2.39)
∂t
whre
∇S
⃗v = = 0, (2.40)
m
where S is the phase of state.
18 CHAPTER 2. QUANTUM DYNAMICS

2.5 Propagators and Feynman Path Integrals

We strat with a evaluated state
iH(t−t0 )
|α, t; t0 ⟩ = e− ℏ |α, t0 ⟩, (2.41)
and we project it into position space
∫ ∑
ψ(x′′ , t) = ⟨x′′ |α, t; t0 ⟩ = dx′ ⟨x′′ |a′ ⟩⟨a′ |x′ ⟩⟨x′ |α, t; t0 ⟩
∫ (2.42)
= dx′ K(x′′ , t; x′ , t0 )ψ(x′ , t0 ),

where the kernel of integral operator is propagator

∑ iE ′ (t−t0 )
K(x′′ , t; x′ , t0 ) ≡ ⟨x′′ |a′ ⟩⟨a′ |x′ ⟩e−
a
ℏ , (2.43)

and we can clearly see that: the wavefunction in (x′′ , t) can be viewed as the
surperposition of others in different position on t0 . We will later prove that the
propagater meets Schrodinger’s equation, and it’s another property is
lim K(x′′ , t; x′ , t0 ) = δ(x′′ − x′ ). (2.44)
t→t0

The strict defination of propegator is

K(x′′ , t; x′ , t0 ) = ⟨x′′ |e−iH(t−t0 )/ℏ |x′ ⟩θ(t − t0 ), (2.45)
where θ is Heviside function. We can calculate the equation of propagator in
time
∂
iℏ K(x′′ , t; x′ , t0 )
∂t ( )
i
= iℏ − ⟨x′′ |He−iH(t−t0 )/ℏ |x′ ⟩θ(t − t0 ) + iℏ⟨x′′ |e−iH(t−t0 )/ℏ |x′ ⟩δ(t − t0 )
ℏ
∫ ∫
iH(t−t0 )
= d3 x⟨x′′ |H|x⟩⟨x|e− ℏ |x′ ⟩θ(t − t0 ) + d3 xiℏ⟨x′′ |x′ ⟩δ(t − t0 )

= H(x′′ )K(x′′ , t; x′ , t0 ) + iℏδ(x′′ − x′ )δ(t − t0 ),

(2.46)
and we need a boundary condition:
K(x′′ , t; x′ , t0 ) = 0 f or t < t0 . (2.47)
We can use Green function to solve this equation, but I don’t want to solve it.
We can understand the propergator in another way with eigenstate
K(x′′ , t; x′ , t0 )
∑ ∑
= ⟨x′′ |a′ ⟩⟨a′ |x′ ⟩e−iH(t−t0 )/ℏ = ⟨x′′ |e−iHt/ℏ |a′ ⟩⟨a′ |eiHt0 /ℏ |x′ ⟩ = ⟨x′′ , t|x′ , t0 ⟩,
(2.48)
we can clearly see that the propergator means the probability that the particle
goes to (x′′ , t) form (x′ , t0 ).
2.5. PROPAGATORS AND FEYNMAN PATH INTEGRALS 19

2.5.1 Feynman Path Integrals

Feynman path integrals is another way of understanding quantum mechanics,

and we will demonstrate that how to derive Schrodinger equation with Feynman
path integrals. Suppose a particle goes to (xN , tN ) from (x1 , t1 ), and we devied
this movement into N parts. Each part has an state |xi , ti ⟩, and the transition
amplitute between |xn , tn ⟩, |xn−1 , tn−1 ⟩ is

1 iS(n,n−1)
⟨xn , tn |xn−1 , tn−1 ⟩ = e ℏ , (2.49)
w(△t)

where w is a weight factor, which is assumed to depend on the time interval

tn − tn−1 , S is the action starting from tn−1 to tn ,

∫ tn
S(n, n − 1) = Ldt. (2.50)
tn−1

Because we have assumed that weight factor is dependent to time interval, we

can derive its expression with free particle,

√
2πiℏ△t (2.51)
⟨xn , tn |xn−1 , tn−1 ⟩ = δ(xn , xn−1 ), ⇒ w(△t) = ,
m

where we use the Gauss integral in calculation. We can write down the transition
amplitude between |xn , tn ⟩ and |x1 , t1 ⟩ with infinitesimal movements,

∫ ∫ ∫ ∏N
m N −1 iS(n,n−1)
⟨xN , tN |x1 , t1 ⟩ = lim ( ) 2 dxN −1 dxN −2 · · · dx2 e ℏ
N →∞ 2πiℏ△t
n=1
∫ xN [ ∫ tN ]
L
= D[x(t)] · exp i dt ,
x1 t1 ℏ
∫ (2.52)
where D is an integral operator, and we multiply all the actions for considering
all possible paths where particle can go through. As for the general situation,
we can derive Schrodinger equation with path integral. We start with

⟨xN , tN |x1 , t1 ⟩
∫
= dxN −1 ⟨xN , tN |xN −1 , tN −1 ⟩⟨xN −1 , tN −1 |x1 , t1 ⟩
∫ √ [( ) ]
m im (xN − xN −1 )2 iV △t
= dxN −1 exp − ⟨xN −1 , tN −1 |x1 , t1 ⟩.
2πiℏ△t 2ℏ △t ℏ
(2.53)
20 CHAPTER 2. QUANTUM DYNAMICS

We assume that time interval and space interval are infinitesimal, meaning xN →
x, tN → t + △t, then we have
∂
⟨xN −1 , tN −1 |x1 , t1 ⟩ → ⟨x, t + △t|x1 , t1 ⟩ = ⟨x, t|x1 , t1 ⟩ + △ ⟨x, t|x1 , t1 ⟩
∫ ∂t
= dξ⟨x, t + △t|x − ξ, t⟩⟨x − ξ, t|x1 , t1 ⟩
√ ∫ ∞ [ ]
m imξ 2 iV △t
= dξexp − ⟨x − ξ, t|x1 , t1 ⟩
2πiℏ△t −∞ 2ℏ△ ℏ
√ ∫ ∞ [ ] ( )
m imξ 2 iV △t
≈ dξexp 1− + ···
2πiℏ△t −∞ 2ℏ△t ℏ
[ ( 2 2 )]
ξ ∂
× ⟨x, t|x1 , t1 ⟩ + ⟨x, t|x1 , t1 ⟩ ,
2 ∂x2
(2.54)
where we drop the linear term of ξ for integral. The first order term of △t is
√ ∫ ∞ [ ][ ]
∂ m imξ 2 iV △t ξ 2 ∂ 2
△t ⟨x, t|x1 , t1 ⟩ = dξexp − + ⟨x, t|x1 , t1 ⟩
∂t 2πiℏ△t −∞ 2ℏ△t ℏ 2 ∂x2
 
√
m  iV △t Γ( 12 ) Γ( 23 ) ∂ 2
 ⟨x, t|x1 , t1 ⟩
= − √ + √
2πiℏ△t ℏ 2 m
2 3 m ∂x
2
2iℏ△t 2iℏ△t

iV △t iℏ
=− ⟨x, t|x1 , t1 ⟩ + ⟨x, t|x1 , t1 ⟩,
ℏ 2m
(2.55)
this is Schrodinger’s equation after mulplying iℏ,
( )
∂ ℏ2
iℏ ⟨x, t|x1 , t1 ⟩ = − + V ⟨x, t|x1 , t1 ⟩. (2.56)
∂t 2m
Chapter 3

Theory of Angular
Momentum

3.1 Rotations and Angular Momentum

We have learned that the Lorentz group has three space rotations and three
boosts, and we list three space rotation matrices in here:

 
1 0 0
Rx (φ) = 0 cos φ − sin φ , (3.1)
0 sin φ cos φ
 
cos φ 0 sin φ
Ry (φ) =  0 1 0 , (3.2)
− sin φ 0 cos φ
 
cos φ − sin φ 0
Rz (φ) =  sin φ cos φ 0 . (3.3)
0 0 1

21
22 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

We also know that the Lorentz group is a nonablian group, but the matrices of
infinitesimal rotations are ablian group, for example:

R x Ry − R y Rx
  2 
1 0 0 1 − ε2 0 ε
= 0 1 − ε2 −ε   0 0 
2
1
ε2 2
0 ε 1− 2 −ε 0 1 − ε2
 2  
1 − ε2 0 ε 1 0 0
− 0 0  0 1 − ε2 −ε 
2
1
2 2
−ε 0 1− 2 ε
0 ε 1 − ε2 (3.4)
 2
  2

ε3
1 − ε2 0 ε 1 − ε2 ε2 ε−
 2 2 3   2
2

= ε 1 − ε2 ε
2 −2ε 
− 0 1 − ε2 −ε 
3 3 2
ε
−ε ε (1 − ε2 )2 −ε ε − ε2 (1 − ε2 )2
2 
0 −ε2 0
≈ ε2 0 0 = Rz (ε2 ) − 1,
0 0 0

where we have neglected the terms of order ε3 , and we can know that when
ε → 0, the commutator will be zero, meaning they are commutative. There are
also similar rotation operations in quantum mechanics, noted as operator D(R),
and the relative equation is

|α⟩R = D(R)|α⟩. (3.5)

We have known that the momentum is the generator of translation, and we can
conclude that the generator of rotation is angular momentum, which is right
scrictly. Then we can easily write down the formula of rotation operator:
( )
iJ · n̂ φ
D(φ) = exp − , (3.6)
ℏ

and we can use Tylor expansion to conculate the commutators between different
angular momentums:
[Ji , Jj ] = iℏεijk Jk . (3.7)

3.2 Spin 1/2 Systems and Finite Rotations

In this section we will study spin 12 system, which is the simplest case. At the
beginning of studying, we write down the state under rotation by finite angle φ
along z-axis:
|α⟩R = Dz (φ)|α⟩, (3.8)
3.2. SPIN 1/2 SYSTEMS AND FINITE ROTATIONS 23

and we are intersted about the expections of spin in different directions,

⟨Sx ⟩ = ⟨α|Dz† Sx Dz |α⟩

( ) ( )
iSz φ iSz φ
= ⟨α| exp Sx exp − |α⟩
ℏ ℏ
( )2
1 iφ 1 iφ
= ⟨α|Sx + [Sz , Sx ] + [Sz , [Sz , Sx ]] + · · · |α⟩
1! ℏ 2! ℏ
( ) ( )
φ2 φ φ3
= ⟨α|Sx 1 − + · · · − Sy − − · · · |α⟩
2! 1! 3!
= ⟨Sx ⟩ cos φ − ⟨Sy ⟩ sin φ,
( ) ( ) (3.9)
iSz φ iSz φ
⟨Sy ⟩ = ⟨α| exp Sy exp − |α⟩
ℏ ℏ
( )2
1 iφ 1 iφ
= ⟨α|Sy + [Sz , Sy ] + [Sz , [Sz , Sy ]] + · · · |α⟩
1! ℏ 2! ℏ
( ) ( )
φ2 φ3
= ⟨α|Sy 1 − + · · · + Sx φ − + · · · |α⟩
2! 3!
= ⟨Sy ⟩ cos φ + ⟨Sx ⟩ sin φ,
⟨Sz ⟩ = ⟨Sz ⟩,

we can see that the expections of spin in x-axis and y-axis have changed after
rotating the state, similar to the rotating x − y plane. And there is another
amazing property of ration operator, because spin is half, the state must rotate
4π if it want to get back to initial state. It’s clear that the rotation is able
to be observed, but I don’t want to explain the details of it in here. Pauli has
introduced the formalism of half spin sytem in 1926, and we simply introduce it.
The eigensate in half spin system is |+⟩, |−⟩ and we use two-component spinors
to replace them:
( ) ( )
1 0
|+⟩ = = χ+ , |−⟩ = = χ− , (3.10)
0 1

and the state can be written in a spinor, and the expection of spin is
∑ ℏ †
⟨Sk ⟩ = ⟨α|Sk |α⟩ = ⟨α|a′ ⟩⟨a′ |Sk |a′′ ⟩⟨a′′ |α⟩ = χ σk χ, (3.11)
2
a′ a′′

where σk is Pauli matrices, and we have mentioned it in QFT, therefore I don’t

want to say it more. But I will prove two properties of it:
• (σ · a)(σ · b) = a · b + iσ · (a × b)
( )
1 1
(σ · a)(σ · b) = σi σj ai bj = {σi , σj } + [σi , σj ] ai bj
2 2 (3.12)
= δij a b + iεijk σ a b = a · b + iσ · (a × b).
i j k i j
24 CHAPTER 3. THEORY OF ANGULAR MOMENTUM
( ) ( ) ( )
• exp − iσ·n̂φ
2 = I cos φ2 − σ · n̂ sin φ2
( ) ( )n
iσ · n̂φ 1 iφ
exp − = − (σ · n̂)n
2 n! 2
[ ] [ ]
1 ( φ )2 1 ( φ )3
= 1− + · · · − iσ · n̂ 1 −
2! 2 3! 2
(φ) (φ)
= I cos − iσ · n̂ sin
( ( φ2) ( )2 (φ) )
cos 2 − inz sin( φ2) (−in
( x)− ny ) sin (2 )
= .
(−ixx + ny ) sin φ2 cos φ2 + inz sin φ2
(3.13)
3.3. SO(3), SU(2) AND EULER ROTATIONS 25

3.3 SO(3), SU(2) and Euler Rotations

The SO(3) is a special orthorgonal group, and the 3 represents degrees of free-
doom, for the elements in SO(3) is symmetric and orthogonal. The SU(2) is
same as SO(3), and the U represents unitary. The element of SU(2) is the form
of ( )
a b
U (a, b) = , U † (a, b) = U (a∗ , −b), |a|2 + |b2 | ≡ 1, (3.14)
−b∗ a∗
It is the general form of 2D rotation.

3.3.1 Euler Rotations

We have learned the Euler rotations of rigid body, an easy method to describe
the rotation of rigid body, for example:

R(α, β, γ) = Rz′ (γ)Ry′ (β)Rz (α), (3.15)

where prime represents the body-fixed axes. But, this kind of expression is not
convenient in quantum mechanics, needed to be expressed in space-fixed axes,
[ ]
R(α, β, γ) = Ry′ (β)Rz (γ)Ry−1
′ (β) Ry ′ (β)Rz (α)

[ ] (3.16)
= Rz (α)Ry (β)Rz−1 (α) Rz (γ + α)
= Rz (α)Ry (β)Rz (γ),

where we use two equations between body-fixed axes and space-fixed axes, but
I don’t want to prove it1 . The corresponding matrix is

D(α, β, γ) = Dz (α)Dy (β)Dz (γ)

( −i(α+γ)/2 )
e cos(β/2) −e−i(α−γ)/2 sin(β/2) , (3.17)
=
ei(α−γ)/2 sin(β/2) ei(α+γ)/2 cos(β/2)

it’s clearly an element of SU(2).

1 More details in P176 of MQM by Sakurai

26 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

3.4 Density Operators and Pure Versus Mixed

Ensembles
What we have learned is allways a single state, and we will study the ensemble in
this section. Firstly, we need to know what is the ensemble: a set that contains
all the possible states. For example, an ensemble has two kinds of states |α⟩, |β⟩,
and each state can be expanded with eigenstate |a′ ⟩ and has its own fractional
population or probability weight, like 70% and 30%. The sum of weight must
equal one. Therefore we can devide the ensemble into the pure ensemble and
mixed ensemble according to the weight.
It’s very similar to stastical physics, we will use statics and quantum me-
chanics to study the ensemble in this section. Because ensemble contains many
states, each state will give a value of observable A, it’s very necessary to define
the ensemble average of A, which is defined by
∑ ∑
[A] ≡ wi ⟨αi |A|αi ⟩ = wi |⟨a′ |αi ⟩|2 , (3.18)
i i,a′

where wi is weight. We can prove that the ensemble average is independent of

the representations:
∑ ∑
[A] = wi ⟨αi |A|αi ⟩ = wi ⟨αi |b′ ⟩⟨b′ |A|b′′ ⟩⟨b′′ |αi ⟩
i i,b′ ,b′′
∑ (3.19)
= ⟨b |ρ|b ⟩⟨b |A|b′′ ⟩ = T r(ρA),
′′ ′ ′

b′ ,b′′

where we define a new matrix, density matrix,

∑
ρ≡ wi |αi ⟩⟨αi |. (3.20)
i

It can be showed that the T r(ρ2 ) is maximal when it’s a pure ensemble and is
less than 1 when it is a mixed ensemble.

3.4.1 Time Evaluation of Ensembles

The defination of density matrix is
∑
ρ= wi |αi ⟩⟨αi |. (3.21)
i

It has to be Hermitian and normalized, which are

ρ† = ρ, tr (ρ) = 1 (3.22)

and now let the state evaluate with time,

|αi ⟩ → |αi , t⟩. (3.23)

3.4. DENSITY OPERATORS AND PURE VERSUS MIXED ENSEMBLES27

So we can derive the time evaluation of density matrix:

∂ρ ∑ ( )
iℏ = wi iℏ∂t |αi , t⟩⟨ai , t| + |αi , t⟩iℏ∂t ⟨αi , t|
∂t i
∑ ( )
= wi H|αi , t⟩⟨αi , t| − |αi , t⟩⟨αi , t|H (3.24)
i
= −[ρ, H]
28 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

3.5 Eigenvalues and Eigenstates of Angular Mo-

mentum
We all know that the angular momentum is the generator of rotation, and the
commutation relations are:

[Ja , Jb ] = iℏεabc Jc [J 2 , Ja ] = 0, (3.25)

the J 2 is the Carsimir operator. And we define two ladder operators:

J± = Jx ± iJy , (3.26)

and the commutation relations are:

[J+ , J− ] = [Jx , −iJy ] + [iJy , Jx ] = ℏJz + ℏJz = 2ℏJz , (3.27)

[Jz , J± ] = [Jz , Jx ] + [Jz , ±iJy ] = iℏJy ± ℏJx = ±ℏJ± , (3.28)
[J , J± ] ≡ 0.
2
(3.29)

We can use these relations to derive the equations of ladder operators, suppose
the equations are:

J+ |j, m⟩ = c+ |j, m + 1⟩, J− |j, m⟩ = c− |j, m − 1⟩, (3.30)

we can use the normalization to calculate the coefficients:

†
⟨j, m + 1|j, m + 1⟩ = ⟨j, m|J+ J+ |j, m⟩ = |c+ |2
= ⟨j, m|J 2 − Jz2 − ℏJz |j, m⟩ = [j(j + 1) − m2 − m]ℏ2
= (j − m)(j + m + 1)ℏ2 ,
†
⟨j, m − 1|j, m − 1⟩ = ⟨j, m|J− J− |j, m⟩ = |c− |2
= ⟨j, m|J 2 − Jz2 + ℏJz |j, m⟩ = [j(j + 1) − m2 + m]ℏ2
= (j − m)(j − m + 1)ℏ2 .
(3.31)
The equations are:
√
J+ |j, m⟩ = (j − m)(j + m + 1)ℏ|j, m + 1⟩, (3.32)
√
J− |j, m⟩ = (j + m)(j − m + 1)ℏ|j, m − 1⟩, (3.33)

and the matrix of J± is

√
⟨j ′ , m′ |J± |j, m⟩ = (j ∓ m)(j ± m + 1)δj ′ j δm′ m±1 , (3.34)
3.5. EIGENVALUES AND EIGENSTATES OF ANGULAR MOMENTUM29

and we can write down the matrices of Jx and Jy with ladder operators:

J+ + J−
⟨j ′ , m′ |Jx |j, m⟩ = ⟨j ′ , m′ | |j, m⟩
2
ℏ ( √ √ )
= δj ′ j (j − m)(j + m + 1)δm′ m+1 + (j + m)(j − m + 1)δm′ m−1 ,
2
J+ − J−
⟨j , m′ |Jy |j, m⟩ = ⟨j ′ , m′ |
′
|j, m⟩
2i
ℏ ( √ √ )
= δj ′ j (j − m)(j + m + 1)δm′ m+1 − (j + m)(j − m + 1)δm′ m−1 .
2i
(3.35)

3.5.1 Representation of Rotation

The representation of 3D rotation is D(R), and it is a Lie group. Its inverse is

Dm′ m (R−1 ) = Dmm

∗
′ (R). (3.36)

The representation of rotation can be expanded with eigenstates2 :

∑ ∑
D(R)|j, m⟩ = |j, m′ ⟩⟨j, m′ |D(R)|j, m⟩ = |j, m′ ⟩Dm
j
′ m (R), (3.37)
m′ m′

the matrix of representaion is

( ) ( ) ( )
j ′ iJz α iJy β iJz γ
Dm ′ m (α, β, γ) = ⟨j, m | exp − exp − exp − |j, m⟩
ℏ ℏ ℏ
′
= e−i(m α+mγ) djm′ m (β),
(3.38)
where we define a new matrix,
( )
′ iJy β
djm′ m (β) = ⟨j, m | exp − |j, m⟩, (3.39)
ℏ

because we have the matrix of Ly and we can calculate the Tylor expansion of
exp(−iJy β/ℏ), and Finally derive the representaion of rotation.

2 We denote D(R) to the representation of rotation for any j, not only for 1
2
30 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

3.6 Orbital Angular Momentum

We will derive the eigenequation of angular momentum in this section. Firstly,
the nabla operator in spherical coordinate is
∂ 1 ∂ 1 ∂
∇ = r̂ + θ̂ + φ̂ , (3.40)
∂r r ∂θ r sin θ ∂φ
and we can get the expression of angular momentum in spherical coordinate by
taking it into the defination of angular momentum in classical physics:
( )
∂ 1 ∂
L = r × p = −iℏ φ̂ − θ̂ . (3.41)
∂θ sin θ ∂φ

We can expand θ̂ and φ̂ in Cartesian coordinate:

θ̂ = cos θ cos φ î + cos θ sin φ ĵ − sin θ k̂,

(3.42)
φ̂ = − sin φ î + cos φ ĵ.

We can clearly derive the components of angular momentum in Cartesian coor-

dinate: ( )
∂ ∂
Lx = −iℏ − sin φ − cos φ cot θ ,
∂θ ∂φ
( )
∂ ∂
Ly = −iℏ cos φ − sin φ cot θ , (3.43)
∂θ ∂φ
∂
Lz = −iℏ .
∂φ
The ladder operators are:
( )
∂ ∂
L± = ±ℏe±iφ ± i cot θ , (3.44)
∂θ ∂φ

We can use ladder operators and Lz to write down the expression of L2 :

[ ( ) ]
1 ∂ ∂ 1 ∂2
L = −ℏ
2 2
sin θ + , (3.45)
sin θ ∂θ ∂θ sin2 θ ∂φ2
the eigenequation of angular momentum is:
[ ( ) ]
1 ∂ ∂ 1 ∂2
⟨x′ |L2 |j, m⟩ = −ℏ2 sin θ + ⟨x′ |j, m⟩ = ℏ2 j(j+1)⟨x′ |j, m⟩.
sin θ ∂θ ∂θ sin2 θ ∂φ2
(3.46)
We have known that the eigenfunction of angular momentum in position is
spherical harmonic function, so we can find the expression with these functions.
Firstly, as for any state, we can get it with rotation, which is
∑
|n⟩ = D(R)|z⟩ = D(φ, θ, 0)|z⟩ = D(R)|l, m⟩⟨l, m|z⟩. (3.47)
lm
3.6. ORBITAL ANGULAR MOMENTUM 31

⟨l, m|z⟩ is the harmonic function with θ = 0, which is

√
∗ 2l + 1
⟨l, m|z⟩ = Ylm (0)δm0 = δm0 . (3.48)
4π
Thus, back to (3.47), we can get
√
∑ 2l + 1 l
′ ∗
⟨l, m |n⟩ = Ylm (θ, φ) = l
Dm ′ m (R)⟨l, m|z⟩ = Dm′ 0 (R) (3.49)
4π
lm
32 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

3.7 Schrodinger’s Equation for Central Poten-

tials
The Hamiltonian of this problem is

p2
H= + V, (3.50)
2m
it’s easy to varify that:
[L, H] = 0, (3.51)
which means L and H share a set of simultaneous eigenstates. We can use the
saperation of variables to get the radial differential equation:
[ ]
ℏ2 d 2 d l(l + 1)h2
− (r ) + + V REl (r) = EREl (r), (3.52)
2mr2 dr dr 2mr2

we can use the following transofmation to reduce the equation:

uEl (r)
REl (r) = , (3.53)
r
the reduced equation is
[ ]
ℏ2 d 2 l(l + 1)ℏ2
− u El + + V uEl = EuEl . (3.54)
2, dr2 2mr2

And the effective potential is

l(l + 1)ℏ2
VEf f (r) ≡ V + . (3.55)
2mr2
The applications in this section is so trivil that I don’t want to talk about it. If
you are interested about this section, you can read this part in another textbook,
Introduction to Quantum Mechanics by Griffiths.
3.8. ADDITION OF ANGULAR MOMENTA 33

3.8 Addition of Angular Momenta

Considering two angular-momentum operators J1 , J2 in different subspaces, we
can define the total angular momentum with direct product:

J ≡ J1 ⊗ 1 + 1 ⊗ J2 , (3.56)

where 1 stands for the identity operator in the infinite-dimensional ket space.
It’ clear that total angular momentum satisfies the cummutation relation:

[Ja , Jb ] = iεabc Jc . (3.57)

We have two choices of basis ket:

• Simultaneous eigenkets of J21 , J22 , J1z , J2z , denoted as |j1 , j2 ; m1 , m2 ⟩.

• Simultaneous eigenkets of J2 , J21 , J22 , Jz , denoted as |j1 , j2 ; j, m⟩.

It’s easy to varify that:

J2 = (J1 + J2 ) · (J1 + J2 ) = J21 + J22 + 2J1 · J2

(3.58)
= J21 + J22 + 2J1z J2z + J1+ J2− + J1− J2+ ,

and easy to varify that:

[J2 , J1z ] ̸= 0, [J2 , J2z ] ̸= 0. (3.59)

For we have two options of basis kets, the transformation of these two basis with
completeness,
∑
|j1 , j2 ; j, m⟩ = |j1 , j2 ; m1 , m2 ⟩⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩, (3.60)
m1 ,m2

where transformation matrix is called Clebsch-Gordon coefficients. The CG

coefficient doesn’t vanish when

m = m1 + m2 , |j1 − j2 | ≤ j ≤ j1 + j2 . (3.61)

To prove this, we have

⟨j1 , j2 ; m1 , m2 |Jz − J1 − J2 |j1 , j2 ; j, m⟩ = (m − m1 − m2 )⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩.

(3.62)
We usually make CG coefficients to be real, and we can write down the orthogo-
nality condition with the fact that the real unitary matrix is orthogonal (I don’t
know until now),
∑
⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩⟨j1 , j2 ; m′1 , m′2 |j1 , j2 ; j, m⟩ = δm1 ,m′1 δm2 ,m′2 ,
j,m
(3.63)
34 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

we can understand this equation from this view: when we sum over j and m, we
obtain the components of |j1 , j2 ; m1 , m2 ⟩ and |j1 , j2 ; m′1 , m′2 ⟩. If these two bases
are same, they are inverse to each other; if not, the product is zero. Similarly,
we can derive another orthogonality condition:
∑
⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j ′ , m′ ⟩ = δj,j ′ δm,m′ .
m1 ,m2
(3.64)
The CG coefficient can be written in terms of Wigner’s 3-j symbol:
( )
√ j1 j2 j
⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩ = (−1)j1 −j2 +m 2j + 1 . (3.65)
m1 m2 −m

We have known the orthogonality relation, and we can derive the third CG
coefficient if we know two coefficients. Firtstly, we operate ladder operators on
state,

J± |j1 , j2 ; j, m⟩
√
= (j ∓ m)(j ± m + 1)|j1 , j2 ; j, m ± 1⟩
∑
= (J1± + J2± ) |j1 , j2 ; m′1 , m′2 ⟩⟨j1 , j2 ; m′1 , m′2 |j1 , j2 ; j, m⟩
m′1 ,m′2
∑ (√
= (j1 ∓ m′1 )(j1 ± m′1 + 1)|j1 , j2 ; m′1 ± 1, m′2 ⟩⟨j1 , j2 ; m′1 , m′2 |j1 , j2 ; j, m⟩
m′1 ,m′2
√ )
+ (j2 ∓ m′2 )(j2 ± m′2 + 1)|j1 , j2 ; m′1 , m′2 ± 1⟩⟨j1 , j2 ; m′1 , m′2 |j1 , j2 ; j, m⟩ ,
(3.66)
we can derive the component of |j1 , j2 ; m1 , m2 ⟩:
√
(j ∓ m)(j ± m + 1)⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩
√
= (j1 ∓ m1 + 1)(j1 ± m1 )⟨j1 , j2 ; m1 ± 1, m2 |j1 , j2 ; j, m⟩ (3.67)
√
+ (j2 ∓ m2 + 1)(j2 ± m2 )⟨j1 , j2 ; m1 , m2 ± 1|j1 , j2 ; j, m⟩,

it’s clear that the (m1 , m2 ) will connect (m1 ±, m2 ) and (m1 , m2 ± 1). Finally,
we can derive other CG coefficients with ladder operators with two known co-
efficients.

3.8.1 CG Coefficients and Rotation Matrices

We have said that the addition of angular momentum corresponds to the dirct
product the rotation representation, labeled with j. |j1 , j2 ; m1 , m2 ⟩ corresponds
to D(j1 ) D(j2 ) and |j1 , j2 ; j, m⟩ corresponds to D(j) , the relation between two
3.8. ADDITION OF ANGULAR MOMENTA 35

representations is:
(j ) (j )
Dm11 ,m′ (R)Dm22 ,m′ (R)
∑
1 2

⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩⟨j1 , j2 ; m′1 , m′2 ; j1 , j2 ; j, m′ ⟩Dm,m′ (R).

(j)
=
j,m,m′
(3.68)
We can prove this equaiton, the left-handed side of equation is

LHS = ⟨j1 , j2 ; m1 , m2 |D(R)|j1 , j2 ; m′1 , m′2 ⟩

= ⟨j1 , m1 |D(j1 ) (R)|j1 , m′1 ⟩⟨j2 , m2 |D(j2 ) (R)|j2 , m′2 ⟩ = Dm11 ,m′ (R)Dm22 ,m′ (R),
(j ) (j )
1 2
(3.69)
and the right-handed side of equation is

RHS = ⟨j1 , j2 ; m1 , m2 |D(R)|j1 , j2 ; m′1 , m′2 ⟩

∑
= ⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩⟨j1 , j2 ; j, m|D(R)|j1 , j2 ; j ′ , m′ ⟩⟨j1 , j2 ; j, m|j1 , j2 ; m1 , m′2 ⟩
j,j ′ ,m,m′
∑
⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m⟩⟨j1 , j2 ; j ′ , m′ |j1 , j2 ; m1 , m′2 ⟩Dm,m′ (R)δj,j ′
(j)
=
j,j ′ ,m,m′
∑
⟨j1 , j2 ; m1 , m2 |j1 , j2 ; j, m′ ⟩⟨j1 , j2 ; j, m|j1 , j2 ; m1 , m′2 ⟩Dm,m′ (R),
(j)
=
j,m,m′
(3.70)
if we let CG coefficient be real, we prove this equation3 .

3 The Schinger’s Oscillatro model is so boring, and it is totally an artificial model, without

any physical meaning. So I just skip this section.

36 CHAPTER 3. THEORY OF ANGULAR MOMENTUM

3.9 Tensor Operators

This section is so boring and tedious, and I only know that the spheircal tensor
operator can explain the selection ruls. So I maybe write a little and don’t want
to write the provement of theorem. The definiation of spherical tensor, which is
m=q
Tqk ≡ Yl=k (V), (3.71)

where the Yqk is the spherical tensor with rank k and magnetic quantum number
m=q
q, and the Yl=k is the artifical spherical harmonic function with vector V, since
the standard spherical harmonic function is the unit vector n̂4 . And the two
important relative commutation relationships are:
[ ] √
[Jz , Tqk ] = qℏTqk , J± , Tqk = (j ∓ q) (j ± q + 1)ℏTq±1
k
. (3.72)

After complicated calculation, we can find the selection rules:

△m = m′ − m = ±1, 0, △j = j ′ − j = ±1, 0. (3.73)

4 That’s the boring thing because this defination is not mathematically well, maybe ill.
Chapter 4

Symmetry in Quantum
Mechanics

4.1 Parity
The transformations of parity and time reversal are detialed disscused in the
chapter 4 of the lecture of Quantum Field Thoery, so we only show the trans-
formation of different quantities in here without provement.


 U (P)JU † (P) = J; (4.1a)

 U (P)xU † (P) = −x; (4.1b)

 U (P)PU †
(P) = −P; (4.1c)

 †
U (P)D(R)U (P) = D(R). (4.1d)

If we use spherical coordinate, the transformations of position and state are

r → r, θ → π − θ, φ → π + φ, |α, l, m⟩ → (−1)l |α, l, m⟩. (4.2)

As for the simple harmonic ocillator, it has (−1)n parity, for

√
mω ip
a† = (x + ), U (P)a† U † (P) = −a† . (4.3)
2ℏ mω

And there are an important conclusion:

The metrix element of odd parity operator don’t vanish when the operator
is contracted with opposite parity states; And the even parity is connected with
same parity states. It is the general form of Laporte rules.

37
38 CHAPTER 4. SYMMETRY IN QUANTUM MECHANICS

4.2 Time Reversal

The time reversal tansformation of relative quantities are:


 U (T )JU † (T ) = −J; (4.4a)

 U (T )xU † (T ) = +x; (4.4b)

 U (T )PU † (T ) = −P; (4.4c)


U (T )D(R)U † (T ) = D(R). (4.4d)

And if we act U (T ) on wave function, which are

∫ ∫
ψ(x) → ψ ∗ (x), U (T )|α⟩ = dxU (T )⟨x|α⟩|x⟩ = dx⟨x|α⟩∗ U (T )|x⟩. (4.5)

U (T )|l, m⟩ = ηm (−1)j−m |l, −m⟩, U 2 (T )|l, m⟩ = (−1)2j |l, m⟩. (4.6)

where ηm is a phase factor of m. The equation of U (T ) and Hamiltonian H is

− iHU (T )|α⟩ = U (T )iH|α⟩. (4.7)

Chapter 5

Approximation Methods

5.1 Time-Independent Perturbation Theory

5.1.1 Nondegenerate Case
Considering the perturbative Hamiltonian, which is

H = H0 + λV, (5.1)

where λ is a parameter, and V is the perturbative term. Physically, the first

order of |n⟩ is |n0 ⟩, and the second term can be viewed as the superposition of
other eigenstates. So, it’s reasonable to define the complementary projection
operator, which is
ϕn ≡ 1 − |n0 ⟩⟨n0 |, (5.2)
it’s clear that when we act this operator on |n⟩, it will project what we want.
And we define the energy shift as:

△n ≡ En − En0 . (5.3)

In quantum mechanics, we care about two things: eigenstate and eigenvalue.

So, we firstly study how to derive the eigenstates. You can derive the following
equation from Schrodinger equation:
( )
(λV − △n ) |n⟩ = En0 − H0 |n⟩. (5.4)

The left-handed side of this equation doesn’t contain |n0 ⟩ physically, so if we

operate projection operator ϕn on it, we can get nothing but itself:

ϕn (λV − △n ) |n⟩ = (λV − △n ) |n⟩. (5.5)

Therefore the approximation of state is

1
|n⟩ = |n0 ⟩ + ϕn (λV − △n )|n⟩, (5.6)
En0 − H0

39
40 CHAPTER 5. APPROXIMATION METHODS

where we define the reciprocal of matrix is the inverse of matrix. Next, we will
expand the state and energy shift in series of λ, which is
|n⟩ = |n0 ⟩ + λ|n1 ⟩ + λ2 |n2 ⟩ + · · ·
1 ( )
= |n0 ⟩ + 0 ϕn (λV − λ△1n − λ2 △2n − · · · ) × |n0 ⟩ + λ|n1 ⟩ + · · · .
En − H0
(5.7)
Compared to the coefficient of different order-λ, we can find the constraint
equations:
ϕn
O(λ) : |n1 ⟩ = V |n0 ⟩, (5.8)
En0 − H0
( )
ϕn
O(λ2 ) : |n2 ⟩ = V − △ n |n ⟩,
1 1
(5.9)
En0 − H0
··· , (5.10)
where we use ϕn |n0 ⟩ = 0 in each equation. And the equations of energy shift
are:
O(λ) : △1n = ⟨n0 |V |n0 ⟩, (5.11)
ϕn
O(λ2 ) : △2n = ⟨n0 |V |n1 ⟩ = ⟨n0 |V 0 V |n0 ⟩, (5.12)
En − H 0
O(λi ) : △in = ⟨n0 |V |ni−1 ⟩. (5.13)
The first order of energy shift is so trival, so we deal with the second order,
ϕn ∑ 1 ∑ |Vin |2
△2n = ⟨n0 |V 0 V |n0 ⟩ = ⟨n 0
|V |i⟩⟨i|V |n 0
⟩ = .
En − H0 i
En0 − Ei0 i
En0 − Ei0
(5.14)
Finally, we can the general form of eigenstate in perturbation theory:
∑ Vin
|n⟩ = |n0 ⟩ + λ 0 − E0
|i0 ⟩ + · · · . (5.15)
i
E n i

We have worked out eigenstates and eigenvalue simutaneously, and it’s necessary
to normalized it.
( )( )
⟨n|n⟩ = Zn−1 = ⟨n0 | + λ⟨n1 | + · · · |n0 ⟩ + λ|n1 ⟩ + · · ·
∑ |Vni |2
≈ 1 + λ2 ⟨n1 |n1 ⟩ + O(λ3 ) = 1 + λ2
0 2
i (En − Ei ) (5.16)
0

∑ |Vni | 2
∂En
⇒ Z n ≈ 1 − λ2 2 = .
i (En − Ei )
0 0 ∂En0

5.1.2 Degenerate Case

Suppose we have a g−fold degenerate satate, which are |m0 ⟩, with energy ED0
.
And when we open the perturbation, these degenerate satates become nondegen-
erate, composing a new complete set |l⟩, and we assume when λ → 0, |l⟩ → |l0 ⟩.
5.1. TIME-INDEPENDENT PERTURBATION THEORY 41

We define a new projection operator P0 , projecting the state |l⟩ to |m0 ⟩ space,
and the relative complementary projection operator is P1 = 1 − P0 . Then we
can split the Schrodinger equation of |l⟩ into two parts, which is

(E − H0 − λV ) P0 |l⟩ + (E − H0 − λV ) P1 |l⟩ = 0. (5.17)

Multiplying P0 and P1 on the left-handed side of this equation, we can derive

two coupling equations:
( )
E − ED
0
− λP0 V P0 |l⟩ − λP0 V P1 |l⟩ = 0, (5.18)
− λP1 V P0 |l⟩ + (E − H0 − λP1 V ) P1 |l⟩ = 0. (5.19)

To avoid the sigularity when λ → 0, we have:

λ
P1 |l⟩ = P1 P1 V P0 |l⟩. (5.20)
E − H0 − λP1 V P1
Taking it back to (5.18), we can derive the equation contain the zero order of
eigenstate and the first order of eigenvalue, which is
( )
E − ED
0
− λP0 V P0 P0 |l0 ⟩ = 0, (5.21)

then the eigenvalue is the result of the following determinent:

[ ( )]
det V − E − ED 0
= 0. (5.22)
42 CHAPTER 5. APPROXIMATION METHODS

5.2 Time-Dependent Perturbation Theory

5.2.1 Interaction Picture
The interaction picuture has been talked about in QFT, so I will briefly write
down the relative details.

|α, t0 ; t⟩I ≡ eiH0 t/ℏ |α, t0 ; t⟩S . (5.23)

iℏ∂t |α, t0 ; t⟩I = VI |α, t0 ; t⟩I . (5.24)
−iH0 t/ℏ
AI ≡ e iH0 t/ℏ
AS e . (5.25)

We will introduce a general method that can be applied in QM and QFT. We

firstly consider an evaluation operator UI (t, t0 ), which makes state |α, t0 ; t0 ⟩I
evaluate to |α, t0 ; t⟩I , which is

|α, t0 ; t⟩I = U (t, t0 )|α, t0 ; t0 ⟩I , (5.26)

and the equation of evaluation opertor is

iℏ∂t UI (t, t0 ) = VI UI (t, t0 ). (5.27)

It has to meet the initial condition:

UI (t0 , t0 ) = 1. (5.28)

So, we can write down the solution order by order, which is

∫ ( )2 ∫ ∫ t′
i t
′ ′ −i t
′
U (t, t0 ) = 1 − dt VI (t ) + dt dt′′ VI (t′ )VI (t′′ ) + · · · , (5.29)
ℏ t0 ℏ t0 t0

which is called Dyson series. Compared to the expansion of coefficient cn (t) =

⟨n|UI |i⟩ = c0n (t) + c1n (t) + · · · , we can get:

c0n (t) = δni (5.30)

∫ ∫
−i t
−i t
′
c1n (t) = dt⟨n|VI |i⟩ = eiωni t Vni dt′ , (5.31)
ℏ t0 ℏ t0
··· , (5.32)
En −Ei
where ωni ≡ ℏ .
5.3. VARIATIONAL MOTHODS 43

5.3 Variational Mothods

Variational method is a very easy and useful way to estimate the eigenvalue
of ground state. We fisrtly introduce its priciple and the process: Firstly, we
have to propose a test ground state |0̃⟩ which is different to true ground state |0⟩
usually. And we can use this test state to calculate the expection of Hamiltonian,
which is
⟨0̃|H|0̃⟩
H= . (5.33)
⟨0̃|0̃⟩
And we will prove the following:

H ≥ E0 . (5.34)

Proof: The test state can be expanded as

∑
|0̃⟩ = |k⟩⟨k|0̃⟩. (5.35)

Taking it into (5.33),

∑ ∑
|⟨k|0̃⟩|2 Ek K=1 |⟨k|0̃⟩| (Ek − E0 )
2
H= ∑ = ∑ + E0 ≥ E0 . (5.36)
|⟨k|0̃⟩|2 |⟨k|0̃⟩|2

Finally, we can analyze the function to find the lowest value with mathmatics.
44 CHAPTER 5. APPROXIMATION METHODS

5.4 Application
5.4.1 Quadratic Stark Effect
Considering an atom contains a electron, putted into an uniform electric field
along z-aixs. The Hamiltonian is

H = H0 + V, V = −e|E|z. (5.37)

Using (5.11) and (5.14), we can get:

∑ |zkn |2
△n = −e|E|znn + e2 |E|2 + ··· . (5.38)
Ek0 − En0
k

The firsty order is zero since atom doesn’t contain electric dipole, and the second
term is called quadratic Stark effect.

5.4.2 Linear Stark Effect

We consider the linear Stark effect of Hydrogen atom, fixed in an uniform electric
field, the relative potential is

V = −e|E|z. (5.39)

Since the energy rely on priciple quantum number n, the 2s and 2p are degen-
erate states. Using the degenerate perturbation theory, the matrix of potential
is  
0 ⟨2s|V |2p, m = 0⟩ 0 0
⟨2p, m = 0|V |2s⟩ 0 0 0
V =
, (5.40)
0 0 0 0
0 0 0 0
where there are many zero is for the selection rule △m = 01 . The energy shift
is
△1 = ±3ea0 |E|. (5.41)
Since the energy shift is propotional to z, we called it linear Stark effect.

5.4.3 Relativistic Correction

The kinetic energy in special relativity is
√ p2 p4
E= p2 c2 + m2 c4 − mc2 ≈ − , (5.42)
2me 8m3e c2
then we can treat the last term as perturbation, which will give us
[ ]
1 2 4 4 3 1
△nl = − me α Z − 4 + 3 (
1 ) . (5.43)
2 4n n l + 21
1I don’t know why we can’t use △m = ±1 in here.
5.4. APPLICATION 45

5.4.4 Spin-Orbit Interaction

We all know that the electron orbits around the nucleus, generating a magnetic
field, and electron has megnetic momenta, will couple with this magnetic field.
We can also regard it as a perturbation, which is
1 1 dV
HLS = (L · S) , (5.44)
m2e c2 r dr
which will give us:
{
1 1 dV ℏ2 l, j = l + 12
△1nlj = ⟨ ⟩ . (5.45)
2 2
2me c r dr 2 −(l + 1), j = l − 1
2

When we chose Coulomb potential, it becomes:

{
Z 2 α2 l, j = l + 12
△nlj =
1
1 En
0
. (5.46)
2nl(l + 1)(l + 2 ) −(l + 1), j = l − 1
2

5.4.5 Zeeman Effect

When we put the Hydrogen atom in an uniform magnetic field, the Hamiltonian
of electron coupling with external magnetic field is
e|B|
HB = − (Lz + 2Sz ) . (5.47)
2me c
When the magnetic field is very week, this term will become perturbative term,
which give us [ ]
eℏ|B| 1
△1B = − m 1± . (5.48)
2me c 2l + 1
And when the magnetic field become very strong, the spin-orbital interaction
will become perturbative term, which will give us
ℏ2 ml ms 1 dV
⟨HLS ⟩ml ms = ⟨ ⟩. (5.49)
2m2e c2 r dr

5.4.6 Time-Dependent Pertubation

Consider a constant perturbation, which is
{
0, t < 0
V (t) = (5.50)
V, t ≥ 0.

Using (5.30-5.31), we have

c0n (t) = δni ,

∫
i t
′ Vni ( ) (5.51)
c1n (t) = − Vni eiωni t dt′ = 1 − eiωni t .
ℏ t0 En − Ei
46 CHAPTER 5. APPROXIMATION METHODS

The probability is
∫ ∫
|Vni |2
Pi→n (t) = dEn ρ(En )|c1n |2 = 4 dEn sin2 (ωni t) ρ(En ), (5.52)
|En − Ei |2
−Ei
where ρ(En ) is the density of states, and ωni ≡ En2ℏ . When t → ∞, the delta
function emerges, it becomes into
∫ ( )
πt 2π
Pi→n (t) = 4 δ (En − Ei ) |Vni |2 ρ(En ) = |Vni |2 ρ(En )t. (5.53)
2ℏ ℏ

And we can define transition rate, which is

( )
dPi→n 2π
wi→n ≡ = |Vni |2 ρ(En ). (5.54)
dt ℏ

It is called Fermis’ golden rule.

Chapter 6

Scattering Theory

6.1 Scattering as A Time-Dependent Perturba-

tion
Since we have learned the method dealing with scattering process in QFT,
we simply introduce some details: The beginning of scattering is to solve the
equation of evaluation operator U (t, t0 ), which is
iℏ∂t U (t, t0 ) = VI U (t, t0 ). (6.1)
We only expand it to first order, which is
∫
i t
U (t, t0 ) = 1 − U (t′ , t0 )dt′ . (6.2)
ℏ t0
The scattering amplitude is
∫
i∑ t
′
⟨n|U (t, t0 )|i⟩ = δni − eiωnm t Vnm ⟨m|U (t′ , t0 )|i⟩ dt′ , (6.3)
ℏ m t0

where |n⟩ and |i⟩ are final state and initial state, both of them are all eigenstate
of H0 , and we insert a completeness relationship of intermediate state. After
box normalization, the S-matrix is
Sni = δni − 2πδ(En − Ei )Tni . (6.4)
And the differential cross section is
( ) ( )2
dσ mL3
= |Tni |2 . (6.5)
dΩ 2πℏ2
Now, our goal is to work out Tni matrix. As what we have learned from QFT,
Tni is relative to evaluation operator from long before scattering, which is
∫ t
i ′ ′ 1 eiωni t+εt
⟨n|U (t, −∞)|i⟩ = δni − Tni eiωni t +εt dt′ = δni + Tni . (6.6)
ℏ −∞ ℏ −ωni + iε

47
48 CHAPTER 6. SCATTERING THEORY

Taking it into (6.3), we can derive the equation of Tni , which is

∑ Tmi
Tni = Vni + Vnm , (6.7)
m
Ei − Em + iℏε

This is a nonlinear equations system, and it can be viewed as the approximation

of the following equation:
1
T =V +V V + ··· . (6.8)
E − H + iε

To solve this equations, we can insert a intermediate state |ψ + ⟩, and it becomes

Tni = ⟨n|V |ϕ+ ⟩, (6.9)

and the intermediate state is

1
|ψ + ⟩ = |i⟩ + V |ψ + ⟩, (6.10)
En − H0 + iℏε

which is called Lipmann-Schwinger equation. And |ψ − ⟩ state is a very boring

state. To work out the wave function of |ψ + ⟩, we project it into position space,
which is
∫
1
⟨x|ψ + ⟩ = ⟨x|i⟩ + d3 x′ ⟨x| |x′ ⟩⟨x′ |V |ψ + ⟩, (6.11)
En − H0 + iε

where we negelect ℏ for convenience. We will see that there will be a propagator.
We firstly calculate the following equation:

ℏ2 ∑ 1
G(x, x′ ) = ⟨x|k⟩⟨k| |k ′ ⟩⟨k ′ |x′ ⟩
2m ′ En − H0 + iε
k,k

ℏ ∑ ei(x·k−x ·k )
′ ′
2
δk,k′
=
2m ′ L3 ℏ2 k 2 /2m − ℏ2 k ′2 /2m + iε
k,k
1 ∑ i(x−x′ )·k 1 (6.12)
= 3 e
L k 2 − k ′2 + iε
k
∫
1 ′ 1
→ d3 kei(x−x )·k 2
(2π) 3 k − k ′2 + iε
′
1 eik|x−x |
=− ,
4π |x − x′ |

it is the Green function of Helmholtz equation. Then (6.11) becomes:

∫ ′ [ ]
2m 3 ′eik|x−x | ′ + r→∞ eikr ′
⟨x|ψ ⟩ = ⟨x|i⟩ − 2
+
d x ⟨x |V |ψ ⟩ −→ e ik·x
+ f (k , k) ,
ℏ 4π|x − x′ | r
(6.13)
6.1. SCATTERING AS A TIME-DEPENDENT PERTURBATION 49

containing the combination of initial state and spherical wave, and f (k ′ , k) is

called scattering amplitude, which is

mL3 ′
f (k ′ , k) = − ⟨k |V |ψ + ⟩. (6.14)
2πℏ2
Then the cross section becomes:
dσ
= |f (k ′ , k)|2 . (6.15)
dΩ
And the optical theorem is:
kσtotal
Imf (k ′ , k) = . (6.16)
4π
After above discussion, we reduce the scattering to solving scattering amplitude,
using (6.8), we can attack the scattering order by order, called Born approxima-
tion. What’s meaning of this process physically? The first order conrresponds
to the particles are scatted once in the scattering region; and the second order
corresponds to be scatterd twice; so does to higher order.
50 CHAPTER 6. SCATTERING THEORY

6.2 Partial Waves

Usually, we allways expand the wave with plane waves, but, from the previous
section, we know that expand with spherical waves is appropriate. Therefore,
we will talk about how to expand the plane wave with spherical wave. Let
|k⟩ represents plane wave in momentum space and |E, l, m⟩ represents spherical
wave. Physically think, if a plane wave propagates along z-aixs, the magnetic
quantum number must zero, since its angular momentum couldn’t have z com-
ponent. Therefore is can be expanded as:
∑∫
|kz⟩ = dE|E, l, m = 0⟩⟨E, l, m = 0|kz⟩. (6.17)
l

Then we can use rotation to obtain the plane wave propagating along any ori-
entation, which is
|k⟩ = D(φ, θ, 0)|kz⟩. (6.18)
Projecting the |E, l, m⟩ component, which is
∑∫
⟨E, l, m|k⟩ = dE ′ ⟨E, l, m|D(φ, θ, 0)|E ′ , l′ , m = 0⟩⟨E ′ , l′ , m = 0|kz⟩
l′
∑∫
= dE ′ Dm0
l
(φ, θ, 0)δll′ δ (E ′ − E) ⟨E ′ , l′ , m = 0|kz⟩
l′
√
l 4π
= Dm0 (φ, θ, 0)⟨E, l, m = 0|kz⟩ = Y l∗ (θ, φ),
2l + 1 m
(6.19)
where we use (3.49), and this equation is the azimuthal function, and it has to
contain the norm of k, which is

⟨k|E, l, m⟩ = glE (k)Yml (θ, φ). (6.20)

So, how to find this radial function? We using the following equation:
( 2 2 )
ℏ k
⟨k| (H0 − E) = − E ⟨k|, (6.21)
2m

and multiplying |E, l, m⟩ on the right, which is

( )
ℏ2 k 2
− E ⟨k|E, l, m⟩ = 0. (6.22)
2m

It’s clear that only if E = ℏ2 k 2 /2m, ⟨k|E, l, m⟩ can not be zero. To better load
this property, we can assume radial function is:
( 2 2 )
ℏ ℏ k
glE (k) = √ δ −E . (6.23)
mk 2m
6.2. PARTIAL WAVES 51

It has been normalized, the plane wave can be expanded as:

∑∫
|k⟩ = dE|E, l, m⟩⟨E, l, m|k⟩. (6.24)
l,m

And we can also expand the plane wave in position space, |x⟩, just use a liitle
complicated math. But I don’t want to show here, just directly give the result,
which is: √
il 2mk
⟨x|E, l, m⟩ = jl (kr)Yml (θ, φ), (6.25)
ℏ π
where jl (kr) is the spherical Bessel function.