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Quantum Mechanics II Lecture Notes

The document outlines the syllabus for PHY 3203: Quantum Mechanics II, covering topics such as Quantum Dynamics, Approximation Methods, Angular Momentum, the Hydrogen Atom, and Introduction to Two Level Systems. It includes detailed sections on time evolution operators, coherent states, and various approximation techniques like the variational method and perturbation theory. Additionally, it addresses angular momentum concepts and the solutions to the Schrödinger equation for the hydrogen atom, along with exercises for each chapter.

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0% found this document useful (0 votes)

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Quantum Mechanics II Lecture Notes

Uploaded by

anywar jimmy

Available Formats

Download as PDF, TXT or read online on Scribd

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PHY 3203: Quantum Mechanics II

Contents

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1 Quantum Dynamics 1
1.1 Time Dependence of Operators (Heisenberg Picture) . . . . . . . . . . . 1
1.1.1 Time Evolution Operator . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Heisenberg Equation of Motion . . . . . . . . . . . . . . . . . . . 2
1.2 Evolution of x̂ and p̂ in the Harmonic Oscillator . . . . . . . . . . . . . . 3
1.2.1 Evolution of â and â† . . . . . . . . . . . . . . . . . . . . . . . . . 3

No
1.2.2 Evolution of x̂ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.3 Evolution of p̂ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Coherent States of the Harmonic Oscillator . . . . . . . . . . . . . . . . . 5
1.3.1 Expansion of Coherent States in terms of Number States . . . . . 5
1.3.2 Non Orthogonality . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.3 Expectation values of x̂ and p̂, and Uncertainty . . . . . . . . . . 8
1.3.4 Time Evolution of Coherent States . . . . . . . . . . . . . . . . . 10
1.4 Chapter Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
ure
2 Approximation Methods 12
2.1 The Variational Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2 Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 Time Independent Perturbation Theory . . . . . . . . . . . . . . . 15
2.2.2 Time Dependent Perturbation Theory . . . . . . . . . . . . . . . 23
2.3 Scattering, Born Approximation and its Applications . . . . . . . . . . . 29
2.3.1 Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.2 Born Approximation . . . . . . . . . . . . . . . . . . . . . . . . . 32
ct

2.4 Chapter Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

3 Angular Momentum 46
3.1 Orbital Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.1.1 Commutation Relations of Angular Momentum Components . . . 47
Le

3.1.2 Lowering and Raising Operators of L̂ . . . . . . . . . . . . . . . . 49

3.1.3 Simultaneous Eigenstates/functions of L̂2 and L̂z . . . . . . . . . 50
3.2 Spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.2.1 Spin 12 and Matrix Elements of Spin Angular Momentum Components 55
3.2.2 Pauli Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.3 Transitions between Eigen States of Ŝz . . . . . . . . . . . . . . . 60
3.2.4 Action of the Lowering and Raising Operators of Ŝ on the Eigen
States of Ŝz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3 Total Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . 62

tes
ˆ
3.3.1 Lowering and Raising Operators of J⃗ . . . . . . . . . . . . . . . . 63
3.4 Addition of Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . 65
3.5 Chapter Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

4 The Hydrogen Atom 72

4.1 Solutions to the Schrodinger Equation by Separation of Variables . . . . 74
4.1.1 Solutions of R(r), f (θ) and g(ϕ) Equations (Radial and Angular

No
Eigenfunctions) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.2 Quantum Numbers l, n and ml . . . . . . . . . . . . . . . . . . . . . . . 93
4.2.1 Principal Quantum Numbers (n) . . . . . . . . . . . . . . . . . . 93
4.2.2 Angular Momentum/Azimuthal/Orbital Quantum Number (l) . . 94
4.2.3 Magnetic Quantum Number ml . . . . . . . . . . . . . . . . . . . 95
4.3 The Spin Quantum Number (s) and the Pauli Exclusion Principle . . . . 95
4.3.1 The Spin Quantum Number (s) . . . . . . . . . . . . . . . . . . . 95
4.3.2 The Pauli Exclusion Principle . . . . . . . . . . . . . . . . . . . . 95
4.4 Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
ure
4.5 The Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.5.1 Anomalous Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . 101
4.5.2 Strong Zeeman Effect . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.6 Chapter Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

5 Introduction to Two Level Systems 106

5.1 Matrix Form of the Schrodinger Equation in a Basis of Finite Dimensions 106
5.2 Two-Base States of a System . . . . . . . . . . . . . . . . . . . . . . . . . 106
ct

5.3 The Ammonia Molecule . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

5.3.1 Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.3.2 Diagonalizing the Energy Matrix H . . . . . . . . . . . . . . . . . 110
5.4 The Ammonia Maser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
5.4.1 Ammonia Molecule in an External Static Electric Field . . . . . . 114
Le

5.4.2 Effect of the Electric Field . . . . . . . . . . . . . . . . . . . . . . 117

5.4.3 Ammonia Molecule in a Time-Varying Electric Field . . . . . . . 118
5.5 Magnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.5.1 The Resonance Condition (ω = ω0 ) . . . . . . . . . . . . . . . . . 123
5.6 Chapter Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

ii
References 127

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No
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iii
1 Quantum Dynamics

1.1 Time Dependence of Operators (Heisenberg Picture)

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1.1.1 Time Evolution Operator

If the initial state of a system is given by |ψ(t0 )⟩ and after a time t, the state changes to
|ψ(t)⟩, we can examine how these states evolve in time.

The two states can be related by a linear operator Û (t, t0 ) such that;

No
|ψ(t)⟩ = Û (t, t0 ) |ψ(t0 )⟩ (1.1)

Û (t, t0 ) is known as the time evolution operator or propagator.

From equation (1.1) we can infer that;

Û (t, t0 ) = Iˆ (1.2)

where Iˆ is the unit operator.

ure
From the Schrodinger time dependent equation;

∂
iℏ |ψ(t)⟩ = Ĥ |ψ(t)⟩ (1.3)
∂t

Substituting equation (1.1) into equation (1.3) gives;

∂(Û (t, t0 ) |ψ(t0 )⟩)

iℏ = Ĥ(Û (t, t0 ) |ψ(t0 )⟩) (1.4)
∂t
ct

∂ Û (t, t0 ) i
= − Ĥ Û (t, t0 ) (1.5)
∂t ℏ
If Ĥ doesn’t depend on time, integrating equation (1.5) gives;

Ĥ
Û (t, t0 ) = e−i(t−t0 ) ℏ (1.6)
Le

Therefore, equation (1.1) becomes;

Ĥ
|ψ(t)⟩ = e−i(t−t0 ) ℏ |ψ(t0 )⟩ (1.7)

1
For t = t0 , Û (t0 , t0 ) = 1 hence the constant of integration must be equal to 1. Therefore,
the state vector at the finite time t is related to the state vector at t = 0 by the equation;

Ĥ
|ψ(t)⟩ = eit ℏ |ψ(0)⟩ (1.8)

tes
Note that Û (t, t0 ) is a unitary operator since Û (t, t0 )Û † (t, t0 ) = Iˆ
If Ĥ depends on time, the integration of equation (1.5) becomes less trivial.

1.1.2 Heisenberg Equation of Motion

Consider an operator Â(t) defined as;

No
Ĥt Ĥt
Â(t) = ei ℏ Ae−i ℏ (1.9)

which depends explicitly on time t.

Â(t) = Û † ÂÛ (1.10)

Differentiating equation (1.9) with respect to time gives;

!
dÂ(t) iĤ i Ĥt −i Ĥt Ĥt Ĥ Ĥt
= e ℏ Âe ℏ + ei ℏ Â −i e−i ℏ (1.11)
dt
ure
ℏ ℏ

iĤ iÂ
= Â − Ĥ (1.12)
ℏ ℏ
dÂ(t) ih i
= Ĥ, Â(t) (1.13)
dt ℏ
This is the Heisenberg equation of motion. It leads to equations that are formally quite
simillar to the corresponding classical equations.
ct

Heisenberg discovered that it is possible to describe nature with classical equations but
we must realise that [x̂, p̂] = iℏ and it is this little correction to the classical way of doing
things that leads to wonderful phenomena of Quantum Mechanics.
Le

2
1.2 Evolution of x̂ and p̂ in the Harmonic Oscillator
1.2.1 Evolution of â and â†

The Hamiltonian of a harmonic operator in terms of â and â† is given by;

tes

† 1
Ĥ = ℏω â â + (1.14)
2

If â† and â depend on time t, equation (1.14) becomes;

† 1
Ĥ = ℏω â (t)â(t) + (1.15)
2

No
Equation (1.15) is the Hamiltonian equation for the Harmonic oscillator in the Heisenberg
picture. Further more, the commutation relations of â and â† with one another and with
Ĥ retain the same form;
â(t), â† (t) = 1

(1.16)
h i
Ĥ, â(t) = −ℏωâ(t) (1.17)
h i
Ĥ, â† (t) = ℏωâ† (t) (1.18)

From equation (1.13), for Â = â† (t);

ure
dâ† (t) ih i
= Ĥ, â† (t) (1.19)
dt ℏ

dâ† (t)
= iωâ† (t) (1.20)
dt
Solving equation (1.20) gives;
â† (t) = eiωt â† (0) (1.21)
ct

Also, for Â = â(t),

dâ(t) ih i
= Ĥ, â(t) (1.22)
dt ℏ
dâ(t)
= −iωâ(t) (1.23)
dt
Le

Solving equation (1.23) gives;

â(t) = e−iωt â(0) (1.24)

3
1.2.2 Evolution of x̂

If x̂ explicitly depends on time t, then it can be defined by;

iĤt iĤt
x̂e−

tes
x̂(t) = e ℏ ℏ (1.25)

Using,
h i 1 h h ii 1 h h h iii
eÂ B̂e−Â = B̂ + Â, B̂ + Â, Â, B̂ + Â, Â, Â, B̂ + ... (1.26)
2! 3!
2 h h
it h i 1 it ii
x̂(t) = x̂ + Ĥ, x̂ + Ĥ, Ĥ, x̂ + ... (1.27)
ℏ 2! ℏ

No
t (ωt)2 (ωt)3 1 (ωt)4 (ωt)5 1
= x̂ + p̂ − x̂ − p̂ + x̂ + p̂ + ... (1.28)
m 2! 3! mω 4! 5! mω
(ωt)2 (ωt)4 (ωt)3 (ωt)5

1
= x̂ 1 + + + ... + p̂ (ωt) − + + ... (1.29)
2! 4! mω 3! 5!
1
x̂(t) = x̂ cos ωt + p̂ sin ωt (1.30)
mω
dx̂(t)
For dt
,
dx̂(t) ih i
= Ĥ, x̂(t) (1.31)
dt ℏ
ure
i itĤ h i −itĤ
= e ℏ Ĥ, x̂ e ℏ (1.32)
ℏ
dx̂(t) 1
= p̂(t) (1.33)
dt m

1.2.3 Evolution of p̂

If p̂ depends on time t, then p̂(t) = Û † p̂Û

2 h h
it h i 1 it ii
p̂(t) = p̂ + Ĥ, p̂ + Ĥ, Ĥ, p̂ + ... (1.34)
ℏ 2! ℏ

(ωt)2 (ωt)4 (ωt)3 (ωt)5

= p̂ 1 − + + ... − mωx̂ (ωt) − + + ... (1.35)
2! 4! 3! 5!
Le

p̂(t) = p̂(0) cos ωt − mωx̂(0) sin ωt (1.36)

dp̂(t)
For dt
,
dp̂(t) ih i
= Ĥ, p̂(t) (1.37)
dt ℏ
i itĤ h i −itĤ
= e ℏ Ĥ, p̂ e ℏ (1.38)
ℏ
4
p̂2
Recall that Ĥ = 2m
+ 12 mω 2 x̂2 . Therefore,

−iℏmω 2

dp̂(t) iĤt iĤt
= e ℏ x̂e− ℏ (1.39)
dt iℏ

tes
dp̂(t)
= −mω 2 x̂(t) (1.40)
dt

1.3 Coherent States of the Harmonic Oscillator

A coherent state |α⟩ is defined as the eigen state of the lowering/annihilation operator â
with eigenvalues α ∈ C.

No
â |α⟩ = α |α⟩ (1.41)

The eigenvalues are complex since â is anti-Hermitian.

Coherent states play an important role in quantum optics, especially in laser physics. By
giving a good overview of coherent states of laser beams, the states describing a laser
beam can be briefly characterized as having;

1. An indefinite number of photons

2. A precisely defined phase in contrast to a state with fixed particle number when
ure
the phase is completely random.

1.3.1 Expansion of Coherent States in terms of Number States

A coherent state |α⟩ can be expressed in terms of the number states |n⟩ by;
∞
X
|α⟩ = cn |n⟩ (1.42)
n=0
ct

From equation (1.41),

Since n is a dummy index, we can replace n by n + 1

∞ ∞
X X √
cn â |n⟩ = cn+1 n + 1 |n⟩ (1.44)
n=0 n=0

5
We obtain;
∞
X √
αcn − cn+1 n + 1 |n⟩ = 0 (1.45)
n=0

This implies that;

tes
√
αcn − cn+1 n + 1 = 0 (1.46)
√
αcn = cn+1 n + 1 (1.47)

We thus obtain a series of equations;



 c1 = αc0
α2
c2 = √α2 c1 = √ c
2 0

No
α3

α
c3 = c = c
 √ √
3 2 6 0

Generally,
αn
cn = √ c0 (1.48)
n!
Equation (1.42) becomes;
∞
X αn
|α⟩ = c0 √ |n⟩ (1.49)
n=0 n!
Applying the normalizing condition ⟨α|α⟩ gives;
ure
X (α∗ )m αn
|c0 |2 √ ⟨m|n⟩ = 1 (1.50)
n,m m!n!

X |α|2n
|c0 |2 =1 (1.51)
n
n!
2
|c0 |2 e|α| = 1 (1.52)
2
|c0 |2 = e−|α| (1.53)
ct

This gives,
1 2
c0 = e− 2 |α| ei(arbitraryphase) (1.54)

Discarding the phase factor, we get,

1 2
c0 = e− 2 |α| (1.55)

6
Therefore, equation (1.49) becomes;
∞
− 12 |α|2
X αn
|α⟩ = e √ |n⟩ (1.56)
n n!

tes
Where α ranges freely on the complex plane.

Equation (1.57) gives the probability for obtaining a particular energy level n when the
system is in a quantum coherent state.

< n >n
Pα (n) = | ⟨n|α⟩ |2 = e−<n> (1.57)
n!

No
Where < n >= ⟨α| â† â |α⟩ = |α|2 . Also, ∆n2 = |α|2 . This shows that the coherent states
have a poissonian distribution.

1.3.2 Non Orthogonality

Coherent states |α⟩ do not form a proper basis, since they are eigen vectors of a non-
Hermitian operator. In particular, they are not orthogonal.

Let us compute the inner product of two coherent states |α⟩ and |β⟩
ure
∞

|α|2 +|β|2
− 2
X (α∗ )n β m
⟨α|β⟩ = e √ ⟨n|m⟩ (1.58)
n,m m!n!

∞

|α|2 +|β|2
− 2
X (α∗ β)n
=e (1.59)
n
n!

|α|2 +|β|2 −2α∗ β
− 2
⟨α|β⟩ = e (1.60)
ct

Although not orthogonal, their superposition goes to zero as |α − β| since,

|α|2 +|β|2 −2α∗ β |α|2 +|β|2 −2α∗ β
2 − 2
− 2
| ⟨α|β⟩ | = e .e (1.61)

2
| ⟨α|β⟩ |2 = e−|α−β| (1.62)
Le

Also, the set of coherent states is complete.

Z
1
|α⟩ ⟨α| d2 α = 1 (1.63)
π

7
Because of this close relation, any state can be written in terms of coherent state super-
position.

1.3.3 Expectation values of x̂ and p̂, and Uncertainty

tes
For the coherent state |α⟩, the expectation value of x̂ is defined by;

< x̂ >= ⟨α| x̂ |α⟩ (1.64)

Recall that, r
ℏ
â + â†

x̂ = (1.65)
2mω

No
Therefore,
λ
< x̂ >= √ ⟨α| â + â† |α⟩

(1.66)
2
q
ℏ
Where λ = mω

But â |α⟩ = α |α⟩ and ⟨α| â† = α∗ ⟨α|

Therefore, equation (1.66) becomes;

ure
λ
< x̂ >= √ ⟨α| â |α⟩ + ⟨α| â† |α⟩

(1.67)
2

λ
= √ (α ⟨α|α⟩ + α∗ ⟨α|α⟩) (1.68)
2
λ
< x̂ >= √ (α + α∗ ) (1.69)
2
√
< x̂ >= 2λ Re{α} (1.70)
ct

For the momentum operator, the expectation is defined by;

< p̂ >= ⟨α| p̂ |α⟩ (1.71)

Recall that,
Le

r
mℏω †
p̂ = i â − â (1.72)
2
Therefore,
iℏ
< p̂ >= √ ⟨α| â† − â |α⟩

(1.73)
λ 2

8
iℏ
= √ ⟨α| â† |α⟩ − ⟨α| â |α⟩

(1.74)
λ 2
iℏ
= √ (α∗ ⟨α|α⟩ − α ⟨α|α⟩) (1.75)
λ 2

tes
iℏ
= √ (α∗ − α) (1.76)
λ 2
iℏ
= − √ (α − α∗ ) (1.77)
λ 2
√
i 2ℏ
< p̂ >= − (α − α∗ ) (1.78)
2λ
√

No
i 2ℏ
< p̂ >= Im{α} (1.79)
λ
Equations (1.69) and (1.78) gives;

1 1 λ
α= √ < x̂ > +i < p̂ > (1.80)
2 λ ℏ

Now, let us compute ⟨x̂2 ⟩ and ⟨p̂2 ⟩

λ2 2
x̂ 2
= ⟨α| â + â† |α⟩ (1.81)
2
ure
λ2
⟨α| â2 + 2â† â + 1 + â†2 |α⟩

= (1.82)
2
λ2
⟨α| â2 |α⟩ + ⟨α| 2â† â + 1 |α⟩ + ⟨α| â†2 |α⟩

= (1.83)
2
λ2 2
α + 2α∗ α + 1 + α∗2

= (1.84)
2
λ2
x̂2 = (α + α∗ )2 + 1

(1.85)
2
ct

q
From ∆x = ⟨x̂2 ⟩ − ⟨x̂⟩2 ,
s 2
λ2 λ
(α + α∗ )2 + 1 +

∆x = √ (α + α∗ ) (1.86)
2 2
Le

λ
∆x = √ (1.87)
2
Exactly the same variance as the ground state |n = 0⟩.

9
For ⟨p̂2 ⟩,
−ℏ2 † 2
p̂2 =

⟨α| â − â |α⟩ (1.88)
2λ2
−ℏ2
â2 − 2â† â − 1 + â†2 |α⟩

= (1.89)

tes
2λ2
−ℏ2 2
α − 2α∗ α − 1 + α∗2

= 2
(1.90)
2λ
−ℏ2
p̂2 = (α − α∗ )2 − 1

2
(1.91)
2λ
q
But ∆p = ⟨p̂2 ⟩ − ⟨p̂⟩2 ,

No
√
v !2
u
u −ℏ2 − 2iℏ
∆p = t 2 (α − α∗ )2 − 1 −

(α − α∗ ) (1.92)
2λ 2λ

ℏ
∆p = √ (1.93)
λ 2
The uncertainty relation ∆x∆p is given by;

λ ℏ
∆x∆p = √ . √ (1.94)
2 λ 2
ure
ℏ
∆x∆p = (1.95)
2
We can see that all coherent states (no matter what complex values α takes on) are
minimum uncertainty states.

1.3.4 Time Evolution of Coherent States

Let |ψ(t = 0)⟩ = |α0 ⟩ such that;

∞
−|α|2 X an
|ψ(0)⟩ = e 2 √ 0 |n⟩ (1.96)
n=0 n!

∞
−|α|2 an 1
√ 0 e−iω(n+ 2 )t |n⟩
X
|ψ(t)⟩ = e 2 (1.97)
n!
Le

10
Let α(t) = α0 e−iωt
ψ(t) = |α(t)⟩ (1.100)

By this, it remains in a coherent state. But, the value of parameter α changes in time.

tes
1.4 Chapter Exercises
1. Show that coherent states are minimum uncertainty states

2. Evaluate |⟨β|α⟩|2 for coherent states |α⟩ and β. Show that the states |α⟩ and β
become completely orthogonal in the limit |α − β| >> 1.

No
3. A coherent state of a one-dimensional harmonic oscillator is defined to be the eigen-
state of the (non-Hermitian) annihilation operator â;

â |α⟩ = α |α⟩

where α is in general a complex number.

(a) Prove that;
|λ|2 †
|α⟩ = e− 2 eλâ |0⟩

(b) Compute the minimum uncertainty relation for such a state.

ct ure
Le

11
2 Approximation Methods
Most problems in quantum mechanics can not be solved exactly. Exact solutions of the
Schrodinger equation exists only for a few idealized systems hence a need for approxima-

tes
tion methods.

In this chapter, we are going to discuss the variational method, the perturbation theory,
the Born approximation and partial waves analysis approximation methods of solving
quantum systems.

No
2.1 The Variational Method
The variational method provides an estimation of the eigenvalues of the ground state of
a system for which one has only a qualitative idea about the form of the wave function.

This method is based on a simple fact that the average energy of the Hamiltonian Ĥ in
a state represented by an arbitrary wave function has to be greater than or equal to the
ground state energy of the system.

Suppose the wave function is ψ , we wish to prove the above statement.

ure
The expectation value of the Hamiltonian is given as;
D E
Ĥ = ⟨ψ| Ĥ |ψ⟩ (2.1)
Z
= ψ ∗ Ĥψdτ (2.2)

Expanding ψ in terms of the eigen functions ϕn of the Hamiltonian Ĥ gives;

X
ψ= an ϕn (2.3)
n

X
|ψ⟩ = an |ϕn ⟩ (2.4)
n
Le

If |ψ⟩ is not normalized, the expectation value of Ĥ in the state is given as;

D E ⟨ψ| Ĥ |ψ⟩
Ĥ = (2.5)
⟨ψ|ψ⟩

12
D E P |a |2 E
n n n
Ĥ = P 2
(2.6)
n |an |

Replacing all the energies by the lowest eigen value E0 of Ĥ gives;

tes
|an |2
D E P
Ĥ = E0 Pn 2
= E0 (2.7)
n |an |

Summary for the Variational Method

1. Choose judiciously a trial wave function that contain a whole bunch of free param-
eters αi ;
ψ = ψ (α1 , α2 , ....) (2.8)

No
2. Vary the parameter αi until the expectation value of Ĥ is minimized;

∂ < Ĥ >
(2.9)
∂αi

The minimum value determined in this way provides an upper bound to E0 , which will
be close to the actual value if the trial function has a form closely resembling that of the
actual ground state function ψ0 .
ure
Example 2.10
2 ℏ2 d2
Consider a trial function ψ = Ae−αx for a harmonic oscillator Hamiltonian Ĥ = − 2m dx2
+
1 2
2
kx where α is the adjustable parameter. Use the variational method to calculate the
ground state energy.

First, we find the constant A by normalization.

Z ∞ Z ∞
∗ 2
ψ ψdτ = A2 e−2αx dx = 1 (2.10)
ct

−∞ −∞

r
2 π
A =1 (2.11)
2α
14
2α
Le

A= (2.12)
π
D E
We now compute Ĥ
D E
Ĥ = ⟨ψ| Ĥ |ψ⟩ (2.13)

13
21 Z ∞
ℏ2 d2

2α −αx2 1 2 −αx2
= e − + kx e dx (2.14)
π −∞ 2m dx2 2
D E ℏ2 α mω 2
Ĥ = + (2.15)
2m 8α

tes
We now minimize Ĥ by differentiating equation (2.15) with respect to the parameter α
and equating it to zero.
d < Ĥ > ℏ2 mω 2
= − (2.16)
dα 2m 8α2
mω
α= (2.17)
2ℏ
Substituting equation (2.17) into equation (2.15) gives;

No
ℏ2 mω mω 2

D E 2ℏ
Ĥ = + (2.18)
min 2m 2ℏ 8 mω

1 1
= ℏω + ℏω (2.19)
4 4
D E 1
Ĥ = ℏω (2.20)
min 2
To tell the appropriateness of the variational method above, we recall that the energy of
the harmonic oscillator is quantized and it is given by;
ure

1
En = ℏω n + , n = 0, 1, 2, 3, ... (2.21)
2

At t = 0, the lowest (ground state) energy is obtained as E0 = ℏω

2
which agrees with the
result obtained by the approximation of the variational method.

It should be noted that while the variational method exactly determines the ground state
energy above, it is not always the case. It remains an approximation which is exact foe
ct

certain instances and mere approximation in other instances.

It is also necessary to note that the choice of the form of the trial wave function is very
important and decisive in the appropriateness of the approximation of the variational
method.
Le

14
2.2 Perturbation Theory
Perturbation theory is based on the assumption that the problem we wish to solve is in
some sense only slightly different from a problem that can be solved exactly.

tes
In the case where the deviation between the two problems is small, perturbation is suit-
able fro calculating the contribution associated with this deviation; this contribution is
then added as a correction to the energy and the wave function of the exactly solvable
Hamiltonian.

Therefore, perturbation theory builds on the known exact solutions to obtain approximate

No
solutions.

2.2.1 Time Independent Perturbation Theory

Consider a time independent Hamiltonian Ĥ of a system expressed as;

Ĥ = Ĥ0 + λĤ1 (2.22)

Where Ĥ1 is very small compared to Ĥ0 . Ĥ0 is the Hamiltonian of the unperturbed
system and λĤ1 is a small perturbation. λ is a real parameter (0 ≤ λ ≤ 1) used to
ure
distinguish between the different orders of perturbation.

The corresponding Schrodinger equation is an eigenvalue problem stated as;

Ĥ0 + λĤ1 |ψn ⟩ = En |ψn ⟩ (2.23)

Where |ψn ⟩ are the eigen states of the complete Hamiltonian Ĥ and En are the corre-
sponding eigenvalues.
ct

From equation (2.23), it follows that we are to consider two separate cases depending on
whether the exact solutions of Ĥ0 are non degenerate or degenerate.

Non degenerate Energy Levels

(0)
For non degenerate
E energy eigenvalues, for every En , there corresponds only one eigen
(0)
state ψn
Ĥ0 ψn(0) = En(0) ψn(0) (2.24)

15
E
(0) (0)
Where the exact eigenvalues En and eigen functions ψn are known.

The basic idea of the perturbation is assuming that the perturbed eigenvalues and eigen
states can both be expanded in power series in the parameter λ.

tes
En = En(0) + λEn(1) + λ2 En(2) + ..., (2.25)

|ψn ⟩ = ψn(0) + λ ψn(1) + λ2 ψn(2) + ..., (2.26)

(0)
When λ = 0, theEexpressions (2.25) and (2.26) yields the unperturbed solutions; En = En
(0)
and |ψn ⟩ = ψn .

No
Substituting equation (2.25) and (2.26) in equation (2.23) gives;

ψn(0) + λ ψn(1) + λ2 ψn(2) + ... =

Ĥ0 + λĤ1
(2.27)
En(0) + λEn(1) + λ2 En(2) + ... ψn(0) + λ ψn(1) + λ2 ψn(2) + ...

Equating coefficients of successive powers of λ on both sides of equation (2.27) gives;

Zero order
ure
λ0 ; Ĥ0 ψn(0) = En(0) ψn(0) (2.28)

First order

λ1 ; Ĥ0 ψn(1) + Ĥ1 ψn(0) = En(0) ψn(1) + En(1) ψn(0) (2.29)

Second order

λ2 ; Ĥ0 ψn(2) + Ĥ1 ψn(1) = En(0) ψn(2) + En(1) ψn(1) + En(2) ψn(0)
ct

(2.30)

Third order

λ3 ; Ĥ0 ψn(3) + Ĥ1 ψn(2) = En(0) ψn(3) + En(1) ψn(2) + En(2) ψn(1) + En(3) ψn(0) (2.31)
Le

We can therefore generalize the outcome as;

Ĥ0 ψn(j) + Ĥ1 ψn(j−1) = En(0) ψn(j) + En(1) ψn(j−1) + .... + En(j) ψn(0) (2.32)
E
(1) (2) (1)
Let us now proceed to determine the eigenvalues En , En and ψn from equations

16
(2.29) and (2.30).

First order correction

tes
To obtain the first order
D correction to the energy eigenvalues En , we simply both sides of
(0)
equation (2.29) by ψn .

ψn(0) Ĥ0 ψn(1) + ψn(0) Ĥ1 ψn(0) = ψn(0) En(0) ψn(1) + ψn(0) En(1) ψn(0) (2.33)

ψn(0) Ĥ0 ψn(1) + ψn(0) Ĥ1 ψn(0) = En(0) ψn(0) ψn(1) + En(1) ψn(0) ψn(0) (2.34)

No
ψn(0) Ĥ1 ψn(0) = En(1) (2.35)
D E D E D E
(0) (0) (0) (1) (0) (0) (1)
Since ψn ψn , ψn Ĥ0 ψn and En ψn ψn are both equal to zero. Equation
(2.35) states the first order correction to the energy En ; This implies that the first order
correction is just the expectation value of the perturbing interaction potential in the state
under correction.

Therefore, the energy to the first order perturbation is given as;

En = En(0) + λ ψn(0) Ĥ1 ψn(0) (2.36)

ure
E
(1)
Now, let us determine ψn
E
(0)
Since the unperturbed state ψn form a complete and orthonormal basis, we can expand
E n Eo
(1) (0)
ψn in the ψn basis.

!
X
ψn(1) = (0)
ψm (0)
ψm ψn(1) (2.37)
m
ct

X
ψn(1) = (0)
ψm ψn(1) (0)
ψm (2.38)
m̸=n
D E
(0) (1)
The term m = n does not contribute since ψm ψn = 0.
Le

D E
(0) (1)
The coefficient ψm ψn can be inferred from equation (2.29) by multiplying both sides
D
(0)
by ψm ;
D E
(0) (0)
ψm Ĥ1 ψn
(0)
ψm ψn(1) = (0) (0)
(2.39)
En − Em

17
Substituting equation (2.39) into (2.38) gives;
D E
(0) (0)
X ψm Ĥ1 ψn
ψn(1) = (0) (0)
(0)
ψm (2.40)
En − Em

tes
m̸=n

Therefore, the eigen functions |ψn ⟩ of Ĥ to first order in the λĤ1 can be obtained by
substituting equation (2.40) into equation (2.26)
D (0) (0)
E 
X ψm Ĥ1 ψn
|ψn ⟩ = ψn(0) + 
(0) (0)
(0) 
ψm (2.41)
m̸=n En − Em

No
Second order correction

(2)
To obtain the second
D order correction En to the energies En , we multiply both sides of
(0)
equation (2.30) by ψn .

ψn(0) Ĥ0 ψn(2) + ψn(0) Ĥ1 ψn(1) = ψn(0) En(0) ψn(2) + ψn(0) En(1) ψn(1) + ψn(0) En(2) ψn(0)
(2.42)
(0) (1) (2) (0) (0)
ψn Ĥ1 ψn = En ψn ψn (2.43)
ure
En(2) = ψn(0) Ĥ1 ψn(1) (2.44)

Inserting equation (2.40) into equation (2.44) gives;

D E 2
(0) (0)
X ψm Ĥ1 ψn
En(2) = (0) (0)
(2.45)
m̸=n En − Em

The eigen energy to second order in λĤ1 is obtained by substitution equation (2.45) into
equation (2.25)
ct

D E 2
(0) (0)
X ψm Ĥ1 ψn
En = En(0) + λ ψn(0) Ĥ1 ψn(0) + λ2 (0) (0)
+ ... (2.46)
m̸=n En − Em
Le

E
(2)
We could go on to calculate the second order correction to the state vector ψn , the
third order correction to the energy and so on, but in practice, equation (2.45) is ordi-
narily as far as it is useful to peruse this method.

18
Note; For perturbation theory to work, the corrections it produces must be small.
D E 2
(0) (0)
ψm λĤ1 ψn
(0) (0)
≪ 1, (m ̸= n) (2.47)

tes
En − Em

(0) (0)
If the unperturbed energy levels En and Em were equal(degenerate), then the condition
(2.47) would break down.

Example 2.11 E q
(0) 2 nπ

The unperturbed wave functions for the finite square well are ψn = a
sin a
x .

No
Suppose we perturb the system by simply raising the floor of the well by a constant
amount V0 .
ure
Figure 2.1: Perturbed Finite Square Potential Well

Find the first order correction to the energies.

Sln; Ĥ1 = V0
En(1) = ψn(0) Ĥ1 ψn(0) (2.48)

En(1) = ψn(0) V0 ψn(0) (2.49)

= V0 ψn(0) ψn(0) (2.50)

En(1) = V0 (2.51)

The corrected energy levels are;

En = En(1) + V0
Le

(2.52)

They are simply lifted by the amount V0 . The only surprising thing is that in this case,
the first order yields the exact answer.

19
Example 2.12
Calculate the first order correction to the ground state energy of an anharmonic oscil-
lator of mass m and angular frequency ω subjected to a potential V (x) = 12 mω 2 x2 +
bx4 , where b is a parameter independent of x. The ground state wave function is

tes
−mωx2

1
E
(0)
ψ0 = mω

πℏ
4
e 2ℏ .

Sln;

(1)
E0 = ψn(0) Ĥ1 ψn(0) (2.53)
(1)
E0 = ψn(0) bx4 ψn(0) (2.54)

No
mω 21 Z ∞
−mωx2

4
= b xe ℏ
(2.55)
πℏ −∞

Using;
Z ∞ √
4 3 π 12
x exp(−ax )dx = 5 ,
0 8 a2
mω 21 3√π 1
(1)
E0 = b .2. 5 (2.56)
πℏ 8 a2
(1) 3bℏ2
ure
E0 = (2.57)
4m2 ω 2
Example 2.13
A particle of mass m0 and charge q oscillates a long the x-axis in a one-dimensional har-
monic potential with an angular frequency ω. If an electric filed ϵ is applied along the
x-axis, evaluate the first and second order corrections to the energy of the nth state.
The potential energy due to the field is V = −qϵx̂ and hence the perturbation is Ĥ1 = qϵx̂.

(1)
The first order correction En ,
ct

En(1) = ⟨n| Ĥ1 |n⟩ (2.58)

En(1) = qϵ ⟨n| x̂ |n⟩ (2.59)

21
†
â + â† . Therefore,
ℏ

In terms of â and â , x̂ = 2m0 ω
Le

21
ℏ
En(1) = qϵ ⟨n| â + â† |n⟩ = 0 (2.60)
2m0 ω

En(1) = 0 (2.61)

20
(2)
The second order correction En ,
2
X ⟨m| Ĥ1 |n⟩
En(2) = (0) (0)
(2.62)

tes
m̸=n En − Em

21
But ⟨m| Ĥ1 |n⟩ = qϵ ⟨m| â + â† |n⟩. Here, m can take all integral values except
ℏ
2m0 ω
n. Therefore, the non vanishing terms of m are (n + 1) and (n − 1).

(0) √
Since En = n + 21 ℏω and using the relations ⟨n + 1| â + â† |n⟩ = n + 1 and

√ (0) (0) (0) (0)
⟨n − 1| â + â† |n⟩ = n, also En − En−1 = ℏω, En − En+1 = −ℏω.

No
2 2
!
q 2 ϵ2 ℏ ⟨n + 1| â + â† |n⟩ ⟨n − 1| â + â† |n⟩
En(2) = (0) (0)
+ (0) (0)
(2.63)
2m0 ω En − En+1 En − En−1
√ 2 √ !
q 2 ϵ2 ℏ n+1 ( n)
= + (2.64)
2m0 ω −ℏω ℏω

q 2 ϵ2 ℏ n + 1

n
= + (2.65)
2m0 ω −ℏω ℏω
q 2 ϵ2 ℏ
= (−n − 1 + n) (2.66)
ure
2m0 ω 2 ℏ
q 2 ϵ2
En(2) = − (2.67)
2m0 ω 2
Hence the energy is given to the second order by;

En = En(0) + En(1) + En(2) (2.68)

q 2 ϵ2

1
En = n + ℏω − (2.69)
2 2m0 ω 2
ct

Example 2.14
A particle of mass m moves in a one-dimensional potential well defined by;

 0
 f or − 2a < x < −a, a < x < 2a
Le

V (x) = ∞ f or x > 2a and x < −2a


V0 f or − a < x < a


Treating V0 for −a < x < a as perturbation on the flat bottom box V (x) = 0 for
−2a < x < 2a and V (x) = ∞ otherwise, calculate the energy of the ground state cor-
rected up to the first order.

21
Sln;

The unperturbed energy and wave function of the ground state are;

tes
(0) π 2 ℏ2 (0) 1 πx
E1 = , ψ = √ cos
32ma2 1 2a 4a

(1)
The first order correction En ,

En(1) = ψn(0) Ĥ1 ψn(0) (2.70)

No
D E
(1) (0) (0)
E1 = ψ1 V0 ψ1 (2.71)
Z a 2

(1) 1 πx
E1 = V0 √ cos2 dx (2.72)
−a 2a 4a
V0 a 1
Z πx
= 1 + cos dx (2.73)
2a −a 2 2a
V0 a V0 2a πx
= x|−a + . sin |a (2.74)
4a 4a π 2a −a

(1) V0 V0 1 1
E1 = + = V0 + (2.75)
ure
2 π 2 π
Therefore, the corrected ground state energy is;

π 2 ℏ2

1 1
E1 = + V0 + (2.76)
32ma2 2 π
ct
Le

22
2.2.2 Time Dependent Perturbation Theory

We now suppose a time dependent external perturbation Ĥ1 (t) to the unperturbed Hamil-
tonian Ĥ0 which yields a total time dependent Hamiltonian Ĥ(t) of a system.

tes
Ĥ(t) = Ĥ0 + λĤ1 (t) (2.77)

Let the eigen states of Ĥ0 take the form |ψn ⟩ such that;

Ĥ0 |ψn ⟩ = En |ψn ⟩ (2.78)

If |ψn (t)⟩ denote the quantum state of the perturbed system at time t, the corresponding

No
Schrodinger equation is,

∂ |ψn (t)⟩
iℏ = Ĥ0 + λĤ1 (t) |ψn (t)⟩ (2.79)
∂t

How does Ĥ1 affect the system?. When the system interacts with Ĥ1 , it either absorbs
or emits energy. This process inevitably causes the system to undergo transitions from
one unperturbed state to another.

The main aim of the time dependent perturbation theory consists of answering this ques-
ure
tion; If the system is initially in an unperturbed state |ψn ⟩ of Ĥ0 , what is the probability
that the system will be found at a later time in another unperturbed state |ψm ⟩.

We now need to look for solutions to equation (2.79) in order to prepare ground for an-
swering this question.

The method to solve equation (2.79) is to expand |ψn (t)⟩ in terms of the expansion
coefficients cn (t).
ct

X iEn t
|ψn (t)⟩ = cn (t)e− ℏ |ψn ⟩ (2.80)
n

Substituting equation (2.80) into equation (2.79) gives;

X
dcn (t) − iEn t
cn (t)En + iℏ e ℏ |ψn ⟩ =
Le

n
dt
(2.81)
X iEn t
cn (t)e− ℏ En + λĤ1 |ψn ⟩
n

Because |ψn ⟩ are time independent.

23
Equating the right hand sides of equation (2.81) gives;

X dcn (t) − iEn t X iEn t

iℏ e ℏ |ψn ⟩ = cn (t)e− ℏ λĤ1 |ψn ⟩ (2.82)
n
dt n

tes
Multiplying equation (2.82) by ⟨ψm | from the left gives;
X iEn t X iEn t
iℏ ċn (t) ⟨ψm |ψn ⟩ e− ℏ =λ cn (t) ⟨ψm | Ĥ1 (t) |ψn ⟩ e− ℏ (2.83)
n n

But ⟨ψm |ψn ⟩ = δmn and thus equation (2.83) becomes;

X iEm t X iEn t

No
iℏ ċm (t)e− ℏ =λ cn (t)Ĥmn (t)e− ℏ (2.84)
m n
X X −i(En −Em )t
iℏ ċm (t) = λ cn (t)Ĥmn (t)e ℏ (2.85)
m n
X
iℏċm (t) = λ cn (t)Ĥmn (t)eiωmn t (2.86)
n

(Em −En )
Where Ĥmn (t) = ⟨ψm | Ĥ1 (t) |ψn ⟩ and ωmn = ℏ
. The quantity ωmn is called the
Born angular frequency.
ure
Equation (2.86) is a set of coupled first order differential equations similar to the Schrodinger
equation.

Assuming that the perturbation λĤ1 is weak, we can expand the coefficients cn in powers
of the parameter λ as;

cn = c(0) (1) 2 (2) 3 (3)

n + λcn + λ cn + λ cn + ... (2.87)
ct

Substituting equation (2.87) into equation (2.86) and equating corresponding powers of
λ gives;
ċ(0)
m = 0 (2.88)
1 X
ċ(1)
m = Ĥmn (t)eiωmn t c(0)
n (2.89)
iℏ n
Le

1 X
ċ(2)
m = Ĥmn (t)eiωmn t c(1)
n (2.90)
iℏ n

Generally,
1 X (s)
ċ(s+1)
m = Ĥmn (t)eiωmn t ck (2.91)
iℏ n

24
These equations can now in principle be integrated successively to any given order in the
(0)
perturbation. Equation (2.88) confirms that cn are time independent. It also tells us
that when there is no time dependence on the Hamiltonian, the Scrodinger equation has
a solution given by,

tes
X
ψ= ψn e−iωn t (2.92)
n

Transition Probability

Suppose that the system is initially in a particular unperturbed state |ψa ⟩ of energy Ea ,
Thus we write,
c(0)
n = δna (2.93)

No
Substituting equation (2.93) into equation (2.89) gives

1 X
ċ(1)
m = Ĥma (t)eiωma t (2.94)
iℏ a

(Em −Ea )
Where ωma = ℏ

Integrating equation (2.94) gives the solution to the first order equation as
t
ure
Z
1 ′ ′ ′
c(1)
m = Ĥma (t )eiωma t dt (2.95)
iℏ 0

Z t
i ′ ′ ′
c(1)
m =− Ĥma (t )eiωma t dt (2.96)
ℏ 0

Hence, to the first order, the probability of finding the system in some final energy eigen
state labeled f at time t, given that it is definitely in a different initial state i at a time
t = 0 is;
(1) 2
Pf i = c1f (t) (2.97)
ct

2
i t
Z
′ ′ ′
(1)
Pf i = − Ĥf i (t )eiωf i t dt , (f ̸= i) (2.98)
ℏ 0
(Ef −Ei )

1 ′
Where ωf i = ℏ
= ℏ
⟨ψf | Ĥ0 |ψ f ⟩ − ⟨ψ i | Ĥ 0 |ψ i ⟩ and Ĥf i (t ) = ⟨ψf | Ĥ1 |ψi ⟩
Le

For most problems in Atomic and Nuclear Physics, the first order (2.98) is usually suffi-
cient.

25
Example 2.15

A harmonic oscillator in the ground state is subjected to a perturbation

tes
2
− t2
Ĥ1 = −x̂e t0

Calculate the probability for transition from the ground state, given that

∞
Z r 2
(−αt2 +iωt) π −ω
e dt = −i e 4α
0 α
Sln

No
The probability that a transition to a state f = 1 has occurred is;

(1) 2
P10 = c11 (t) (2.99)

But
Z t
(1) i ′ ′ ′
c1 =− Ĥ10 (t )eiω10 t dt (2.100)
ℏ 0

But
ure
′
Ĥ10 (t ) = ⟨f | Ĥ1 |i⟩ = ⟨1| Ĥ1 |0⟩ (2.101)
2
′ − t2
Ĥ10 (t ) = − ⟨1| x̂ |0⟩ e t0
(2.102)
r 2
′ ℏ − tt2
Ĥ10 (t ) = − e 0 (2.103)
2mω
Substituting equation (2.103)into equation (2.100)
ct

r ′2
Z t
(1) i ℏ −t2 ′ ′
c1 = e t0
eiω10 t dt (2.104)
ℏ 2mω 0

r Z t t′ 2 ′

(1) i ℏ − 2 +iωt ′
c1 = e t0 dt , ω10 = ω (2.105)
ℏ 2mω 0
Le

r
i
q
ℏ −ω 2 2
= . − i πt20 e 4 t0 (2.106)
ℏ 2mω
r
πt20 −ω2 t20
= e 4 (2.107)
2mℏω
(1) 2
P10 = c11 (t) (2.108)

26
(1) πt20 −ω2 t20
P10 = e 2 (2.109)
2mℏω
Example 2.16

Sln
The probability of transition from state |j⟩ to state |k⟩ at a time t is,

No
2
(1) (1)
Pkj = ck (t) (2.110)

Z t 2
i ′ ′ ′
= − Ĥkj (t )eiωkj t dt (2.111)
ℏ 0
Z t 2
(1) i ′ ′
Pkj = − ⟨k| Ĥ1 (t) |j⟩ eiωkj t dt (2.112)
ℏ 0

The probability of transition from state |k⟩ to |j⟩ is,

2
(1) (1)
Pjk = cj (t) (2.113)
ure
Z t 2
i ′ ′ ′
= − Ĥjk (t )eiωjk t dt (2.114)
ℏ 0
Z t 2
(1) i ′ ′
Pkj = − ⟨j| Ĥ1 (t) |k⟩ eiωjk t dt (2.115)
ℏ 0

Since Ĥ1 is Hermitian, ⟨k| Ĥ1 (t) |j⟩ = ⟨j| Ĥ1 (t) |k⟩. Also, it follows that ℏωkj = Ek −Ej =
−ℏωjk .
ct

As the integrand of the second integral is the complex conjugate of that of the first one.
We have,
2 2
(1) (1)
ck (t) = cj (t) (2.116)
Le

(1) (1)
Pkj = Pjk (2.117)

27
Example 2.17
A quantum system is initially in the ground state |0⟩. At t = 0, a perturbation of the
form Ĥ1 (t) = Ĥ0 e−αt , where α is a constant, is applied. Show that the probability that
the system is in a state |1⟩ after a long time is;

tes
2
⟨1| Ĥ0 |0⟩ E1 − E0
P10 = 2
, W here ω10 =
ℏ2 (α2 + ω10 ) ℏ
Rt ′
(1) ′ ′
From cf = − ℏi 0
Ĥf i (t )eiωf i t dt ,

′
Ĥf i (t ) = ⟨ψf | Ĥ1 (t) |ψi ⟩ (2.118)

No
Ĥ10 (t) = ⟨1| Ĥ0 e−αt |0⟩ = ⟨1| Ĥ0 |0⟩ e−αt (2.119)
i t
Z
′ ′ ′
(1)
c1 = − ⟨1| Ĥ0 |0⟩ e−αt eiω10 t dt (2.120)
ℏ 0
As t −→ ∞, equation (2.120) becomes;
Z ∞
i ′ ′
=− ⟨1| Ĥ0 |0⟩ e−(α−iω10 )t dt (2.121)
ℏ 0

i −1 ′
ure
= − ⟨1| Ĥ0 |0⟩ e−(α−iω10 )t |∞
0 (2.122)
ℏ (α − iω10 )
i ⟨1| Ĥ0 |0⟩
=− (2.123)
ℏ (α − iω10 )
2
(1) (1)
P10 = c1 (t) (2.124)
2
⟨1| Ĥ0 |0⟩
(1)
P10 = 2
(2.125)
ℏ2 (α2 + ω10 )
ct
Le

28
2.3 Scattering, Born Approximation and its Applications
2.3.1 Scattering

tes
In a typical scattering experiment, a beam of particles often from an accelerator is pro-
jected at a fixed target composed of other particles; Some particles are reflected and
others transmitted.

In three dimensions, there is more than reflection and transmitted. The experimentalist
counts the number of particles scattered through angles θ and φ that enter a detector
that subtends a certain solid angle as indicated in Figure 2.2.

No
ure
Figure 2.2: Scattering between an incident beam of particles and a fixed target: the scattered
particles are detected within a solid angle dΩ along the direction (θ, φ)

The number of particles scattered into an element of solid angle dΩ is proportional to the
differential cross-section.
ct

dσ

The differential cross-section dΩ is defined as the number of particles scattered into an
element of solid angle dΩ in the direction (θ, φ) per unit time and incident flux.

dσ(θ, φ) 1 dN (θ, φ)
= (2.126)
dΩ jinc dΩ
Le

where jinc is the incident flux.

The total cross-section σ is obtained by integrating equation(2.126) over all angles.

Z
dσ
σ= dΩ (2.127)
dΩ

29
But dΩ = sin θdθdφ Z π Z 2π
dσ(θ, φ)
σ= sin θdθ dφ (2.128)
0 0 dΩ
Note; The dimension of the total cross-section is area. This area may have a simple sig-

tes
nificance in some cases. For example, in a nuclear scattering experiment with neutrons
as the particle projectiles and a nucleus as the target, the total cross section is one the
order of the size of the nucleus since the nuclear force is shorted ranged and neutrons
that strike the nucleus are likely to interact with it.

On the other hand, if neutrinos are the projectiles and the target is a nucleus, the cross
section is many orders of magnitude smaller. This is not because the nucleus has sud-

No
denly shrunk in size but because neutrinos interact so weakly with the nucleus that most
of them pass right through the nucleus without scattering at all.

Scattering Amplitude

⃗
The wave describing the incident particle is ϕinc (⃗r) = Aeik0 .⃗r and scattered wave is
i⃗
k.⃗
r
ϕsc (⃗r) = Af (θ, φ) e r where f (θ, φ) is called the scattering amplitude, ⃗k is the wave
number associated with the scattered particle and θ is the angle between k⃗0 and ⃗k.
ure
After scattering has taken place, the total wave is given by a superposition of the incident
plane wave and the scattered wave.

ψ(⃗r) = ϕinc (⃗r) + ϕsc (⃗r) (2.129)

⃗
ik⃗0 .⃗
r eik.⃗r
= Ae + Af (θ, φ) (2.130)
r
⃗
!
ik⃗0 .⃗
r eik.⃗r
ct

ψ(⃗r) = A e + f (θ, φ) (2.131)

where A is a normalization factor.

Differential Cross-section
Le

Incident flux

iℏ
jinc = (ϕinc ∇ϕ∗inc − ϕ∗inc ∇ϕinc ) (2.132)
2µ

30
⃗
From ϕinc (⃗r) = Aeik0 .⃗r ,
|A|2 ℏk0
ȷinc = (2.133)
µ
where µ is the effective mass.

tes
Scattered flux

iℏ
jsc = (ϕsc ∇ϕ∗sc − ϕ∗sc ∇ϕsc ) (2.134)
2µ
i⃗
k.⃗
r
From ϕsc = Af (θ, φ) e r ,

|A|2 ℏk
jsc = |f (θ, φ)|2 (2.135)

No
µr2
The number of particles dN (θ, φ) scattered into an element of solid angle dΩ in the di-
rection (θ, φ) and passing through a surface element dA = r2 dΩ per unit time is given as;

dN (θ, φ) = jsc r2 dΩ (2.136)

dN
= jsc r2 (2.137)
dΩ
!
|A|2 ℏk 2
= 2
|f (θ, φ)| r2 (2.138)
µr
ure
dN |A|2 ℏk
= |f (θ, φ)|2 (2.139)
dΩ µ
Inserting equation (2.139)into (2.126) gives;
!
dσ(θ, φ) µ |A|2 ℏk
= 2 |f (θ, φ)|2 (2.140)
dΩ |A| ℏk0 µ

dσ(θ, φ) k
|f (θ, φ)|2
ct

= (2.141)
dΩ k0
Since the normalization factor A doesn’t contribute to the differential cross-section, we
will take it equal to 1. For elastic scattering, k0 = k hence,

dσ
= |f (θ, φ)|2 (2.142)
Le

dΩ
dσ
The problem of determining the differential cross-section dΩ
reduces to that of obtaining
the scattering amplitude f (θ, φ).

31
2.3.2 Born Approximation

A particularly good approach for calculating the scattering amplitude when the energy
of the incident beam is large in comparison with the potential energy is the Born approx-

tes
imation.

The scattering amplitude f (θ, φ) can be determined from the solutions of the Schrodinger
equation;
ℏ2 2
− ∇ ψ(⃗r) + V (r)ψ(⃗r) = Eψ(⃗r) (2.143)
2m
Equation (2.143) can be written as;

No
∇2 + k 2 ψ(⃗r) = Q

(2.144)
√
2mE 2m
where k = ℏ
and Q = ℏ2
V ψ(⃗r).

This has the superficial appearance of the Helmholtz equation.

Suppose we could find a function G(⃗r) that solves the Helmholtz equation with a delta
function ”source”.
∇2 + k 2 G(⃗r) = δ 3 (⃗r)

(2.145)
ure
We could express ψ(⃗r) as an integral.
Z
ψ(⃗r) = G (⃗r − ⃗r0 ) Q (⃗r0 ) d3⃗r0 (2.146)

Equation (2.146) satisfy the Schrodinger equation (2.144). To show;

Z
2 2
∇2 + k 2 G (⃗r − ⃗r0 ) Q (⃗r0 ) d3⃗r0

∇ +k ψ(⃗r) = (2.147)
ct

Z
= δ 2 (⃗r − ⃗r0 ) Q (⃗r0 ) d3⃗r0 (2.148)

∇2 + k 2 ψ(⃗r) = Q (⃗r)

(2.149)

What we are trying to do is expressing the Schrodinger equation in integral form rather
Le

than solving it.

G (⃗r) is called the Green’s function for the Helmholtz equation. Derivations (see reference

32
textbooks) show that;
eik|⃗r−r⃗0 |
G (⃗r) = − (2.150)
4π |⃗r − r⃗0 |
We can add it to any function that satisfies the Homogeneous Helmholtz equation.

tes
∇2 + k 2 G0 (⃗r) = 0

(2.151)

Clearly, the result (G + G0 ) satisfies equation (2.146).

Substituting equation (2.150) and the value of G(⃗ r0 ) into equation (2.146) gives;

eik|⃗r−r⃗0 |
Z
m
ψ(⃗r) = − V (⃗r0 ) ψ (⃗r0 ) d3⃗r0 (2.152)
2πℏ2 4π |⃗r − r⃗0 |

No
Now we arrive at the integral form of the Schrodinger equation;

eik|⃗r−r⃗0 |
Z
m
ψ(⃗r) = ψ0 (⃗r) − V (⃗r0 ) ψ (⃗r0 ) d3⃗r0 (2.153)
2πℏ2 4π |⃗r − r⃗0 |

Where ψ0 (⃗r) satisfies the free particle Schrodinger equation (∇2 + k 2 ) ψ0 (⃗r) = 0.

The First Born Approximation

ure
Here, we suppose that V (⃗r) is localized about ⃗r0 = 0 i.e. the potential drops to zero out-
side some finite region and we then calculate ψ(⃗r) at points far away from the scattering
center.

Assuming that |⃗r| >> |⃗r| for all points that contribute to the integral in equation (2.153),

2 2 2⃗r.⃗
r0
|⃗r − r⃗0 | = r + r02 − 2⃗rr⃗0 ≈ r 2
1− 2 (2.154)
r
ct

And hence;
|⃗r − r⃗0 |2 ≈ r − r̂.⃗r0 (2.155)
⃗
Let ⃗k = kr̂, then eik|⃗r−⃗r0 | ≈ eikr .e−ik.r⃗0 and therefore,

eik|⃗r−⃗r0 | eikr −i⃗k.r⃗0

≈ e (2.156)
|⃗r − r⃗0 | r

Therefore, equation (2.153) becomes;

eikr −i⃗k.⃗r0
Z
m
ψ(⃗r) = ψ0 (⃗r) − .e V (⃗r0 ) ψ (⃗r0 ) d3⃗r0 (2.157)
2πℏ2 r

33
In the case of scattering, ψ0 (⃗r) = Aeikz , the incident plane wave. Therefore, our wave
function in (2.157) can be written as;

eikr
Z
ikz m −i⃗k.⃗
r0 3
ψ(⃗r) = Ae +A − e V (⃗r0 ) ψ (⃗r0 ) d ⃗r0 (2.158)

tes
r 2πAℏ2

Therefore,
Z
m ⃗
f (θ, φ) = − e−ik.⃗r0 V (⃗r0 ) ψ (⃗r0 ) d3⃗r0 (2.159)
2πAℏ2
is the scattering amplitude.

No
Let us assume that the potential doesn’t significantly alter the wave function;

⃗′
ψ(⃗r0 ) ≈ ψ0 (⃗r0 ) = Aeikz0 = Aeik .⃗r0 (2.160)

′
For ⃗k = kẑ Then;
Z
m −i⃗k.⃗r0
′
i⃗k .⃗
r0 3
f (θ, φ) = − e V (⃗r 0 ) Ae d ⃗r0 (2.161)
2πAℏ2
Z
m −i⃗k.⃗
r0
′
i⃗k .⃗
r0 3
=− 2
e V (⃗r 0 ) e d ⃗r0 (2.162)
2πℏ
ure
Z
m ′
i(⃗k −⃗k).⃗ r0
f (θ, φ) = − e V (⃗r0 ) d3⃗r0 (2.163)
2πℏ2
′ ′
Let us clarify what are the vectors ⃗k and ⃗k. ⃗k points in the incident direction while ⃗k
in the scattering direction.
ct
Le

Figure 2.3: Wave vectors and direction

34
In particular, for low energy (long wavelength) scattering, the exponential factor in equa-
tion (2.163) is essentially constant over the scattering region and the Born approximation
simplifies to;

tes
Z
m
f (θ, φ) = − V (⃗r) d3⃗r (low energy) (2.164)
2πℏ2

′
⃗ ⃗
If the potential V (⃗r) is spherically symmetric, V (⃗r0 ) = V (r0 ) and k − k .⃗r0 = qr0 cos(θ0 ).
Z
m
f (θ, φ) ≈ − eiqr0 cos(θ0 ) V (r0 ) r02 sin(θ0 )dr0 dθ0 dφ0 (2.165)
2πℏ2
Z
2m
f (θ) ≈ − 2 r0 V (r0 ) sin(qr0 )dr0 (2.166)

No
ℏq
Dropping the subscript on r, we get;
Z
2m
f (θ) = − 2 rV (r) sin(qr)dr (Symmetric potential) (2.167)
ℏq

′
Note; from q = ⃗k − ⃗k ,

′ 2 ′ ′
q 2 = ⃗k − ⃗k = k 2 + k 2 − 2k k cos(θ) (2.168)
ure
′
For quantum scattering, k = k

2 2 θ 2 2
q = 2k (1 − cos(θ)) = 4k sin (2.169)
2

θ
q = 2ksin (2.170)
2
This is referred to as the momentum transfer, which is the amount of momentum one
particle gives to another.
ct

Example 2.18

Use low-energy scattering in Born approximation to calculate the differential and total
cross-section for the low energy soft-sphere scattering.
Le

(
V0 ;r ≤ a
V (⃗r) =
0 ;r > a
Sln;

35
m
R
From f (θ, φ) = − 2πℏ2 V (⃗r) d3⃗r,
Z a
m
f (θ, φ) = − 4πV0 r2 dr (2.171)
2πℏ2 0

tes
m a3
=− (4πV0 ) (2.172)
2πℏ2 3
2ma3
f (θ, φ) = − V0 (2.173)
3ℏ2
dσ
= |f (θ, φ)|2 (2.174)
dΩ
dσ 4m2 a6 2

No
= V (2.175)
dΩ 9ℏ4 0
dσ
R
Total cross-section σ = dΩ
dΩ. But dΩ = sin(θ)dθdφ
Z π Z 2π
dσ
σ= sin θ dφ (2.176)
0 0 dΩ
π 2π
4m2 a6 2
Z Z
= sin θ V dφ (2.177)
0 0 9ℏ4 0
2 6
4m a 2
= 4π V (2.178)
9ℏ4 0
ure
16πm2 a6 V02
σ= (2.179)
9ℏ4
Example 2.19

The scattering amplitude for the first born approximation is given by;
Z ∞
2µ ′
′ ′ ′
f (θ) = − 2 r V r sin qr dr
ℏq 0
ct

where all symbols carry their usual meaning.

If particles are incident on a spherically symmetric potential given by;

e−γr
Le

V (r) = β
r

where β and γ are constants.

a) Show that the differential scattering cross-section for the scattering vector k is given
by;

36
2
dσ 2µβ
=
dΩ ℏ (k 2 + γ 2 )
2

b) Show that the differential scattering cross-section for alpha particles of energy E

tes
and incident on a nucleus of atomic number Z is given by;
!2
dσ Ze2
=
8πϵ0 E sin2 θ

dΩ 2

Sln; (a)
dσ
= |f (θ)|2 (2.180)

No
dΩ
Z ∞ 2
4µ2 ′
′ ′ ′
= r V r sin qr dr (2.181)
ℏ4 q 2 0
−γr
For V (r) = β e r

∞ ∞
e−γr
Z ′ ′ ′ Z
′
r V r sin qr dr = rβ sin(qr)dr (2.182)
0 0 r
Z ∞
= βe−γr sin(qr)dr (2.183)
0
ure
Let u = sin(qr) and dv
dr
= e−γr , du
dr
= q cos(qr) and v = − γ1 e−γr

Solving the integral (equation (2.183)) gives;

Z ∞ Z ∞
−γr β q
βe sin(qr)dr = − e−γr sin(qr)|∞
0 + β e−γr cos(qr)dr (2.184)
0 γ 0 γ
Z ∞
q
= β e−γr cos(qr)dr (2.185)
γ
ct

Also, let Let u = cos(qr) and dv

dr
= e−γr , du
dr
= −q sin(qr) and v = − γ1 e−γr

Therefore;
Z ∞ Z ∞
βq 1 −γr q −γr
Le

−γr ∞
βe sin(qr)dr = − e cos(qr)|0 − e sin(qr)dr (2.186)
0 γ γ 0 γ

q ∞ −γr
Z
βq 1
= − − e sin(qr)dr (2.187)
γ γ γ 0

37
∞
q2
Z
−γr βq
βe sin(qr)dr 1 + 2 = 2 (2.188)
0 γ γ
Z ∞
βq
βe−γr sin(qr)dr = (2.189)
0 γ2 + q2

tes
From equation (2.181)
2
dσ 4µ2 βq
= 4 2 2 (2.190)
dΩ ℏ q γ + q2
4µ2 β 2 q 2
= (2.191)
ℏ4 q 2 (γ 2 + q 2 )2
2
dσ 2µβ
= (2.192)

No
dΩ ℏ2 (γ 2 + q 2 )
θ
. For θ = π3 , q = k

But q = 2k sin 2

2
dσ 2µβ
= (2.193)
dΩ ℏ2 (γ 2 + k 2 )

(b)

′ Z1 Z2 e2 2Ze2
From potential energy V (r ) = 4πϵ0 r
= 4πϵ0 r
ure
ℏ2 k2 1 2µ
Since the energy of the incident particle is proportional to k i.e. E = 2µ
, E = ℏ2 k2

From dσ
dΩ
= |f (θ)|2 ,

∞ 2
4µ2
Z
dσ ′
′ ′ ′
= 4 2 r V r sin qr dr (2.194)
dΩ ℏq 0

But;
∞ ∞
2Ze2
Z ′ ′ ′ Z
′
ct

r V r sin qr dr = r sin(qr)dr (2.195)

0 0 4πϵ0 r
∞
2Ze2
Z
= sin(qr)dr (2.196)
4πϵ0 0

2Ze2
= cos(qr)|∞
0 (2.197)
4πϵ0 q
Le

2Ze2
= (2.198)
4πϵ0 q
2
dσ 4µ2 2Ze2 16µ2 Z 2 e4
= 4 2 = (2.199)
dΩ ℏ q 4πϵ0 q 16ℏ4 q 4 π 2 ϵ20

38
2
µZe2

= (2.200)
ℏ2 q 2 πϵ0
θ
and q 2 = 4k 2 sin2 ( 2θ )

But q = 2k sin 2

tes
!2
dσ µZe2
= (2.201)
4k 2 sin2 ( 2θ ) πϵ0

dΩ ℏ2

!2
µZe2
= (2.202)
4ℏ2 k 2 sin2 ( 2θ )πϵ0
1 µ
But 2E
= ℏ2 k2

No
!2
dσ Ze2
= (2.203)
dΩ 8πϵ0 E sin2 ( 2θ )
Example 2.20

The scattering amplitude for the first Born approximation is given by;
Z ∞
2m ′
′ ′ ′
f (θ) = − 2 r V r sin qr dr
ℏq 0

where all symbols carry their usual meaning.

ure
a) The Yakuwa potential given by;

β −r
e a V (r) =
r
where β and a are constants. Show that the differential cross section is given by;
!
dσ 4m2 β 2 1
=
ct

2
dΩ ℏ4 1
+ q2
a2

b) Show that in the limit of large incident energies where q 2 >> a−2 , the Yakuwa
scattering approximates the Rutherford scattering given by the cross section;
Le

Ze2

dσ 1
=
dΩ 2E sin4 ( 2θ )

Where θ is the scattering angle and E is the kinetic energy of the incident particle.

39
Sln;
(a)

dσ
= |f (θ)|2 (2.204)

tes
dΩ
Z ∞ 2
4m2 ′
′ ′ ′
= r V r sin qr dr (2.205)
ℏ4 q 2 0
r
But V (r) = βr e− a Z ∞
r
= βe− a sin(qr)dr (2.206)
0
r r
Let u = sin(qr) and dv
dr
= e− a , du
dr
= q cos(qr) and v = −ae− a

No
Solving the integral (equation (2.206)) gives;
Z ∞ Z ∞
− ar − ar r
βe sin(qr)dr = −βae sin(qr)|∞
0 + −βae− a .q cos(qr)dr (2.207)
0 0

Z ∞
r
= βaqe− a cos(qr)dr (2.208)
0
r r
Also, let Let u = cos(qr) and dv
dr
= e− a , du
dr
= −q sin(qr) and v = −ae− a
Therefore;
ure
Z ∞ Z ∞
− ar − ar ∞ − ar
βe sin(qr)dr = βaq −ae cos(qr)|0 − aqe sin(qr)dr (2.209)
0 0

Z ∞
− ar
= βaq a − aq e sin(qr)dr (2.210)
0
Z ∞
r
βe− a sin(qr)dr 1 + a2 q 2 = a2 qβ

(2.211)
0
∞
a2 qβ
Z
ct

r
βe− a sin(qr)dr = (2.212)
0 (1 + a2 q 2 )
Therefore;
∞
a2 qβ
Z ′ ′ ′
′
r V r sin qr dr = (2.213)
(1 + a2 q 2 )
Le

And;
2
dσ 4m2 a2 qβ
= 4 2 (2.214)
dΩ ℏ q (1 + a2 q 2 )
4m2 a4 q 2 β 2
= . (2.215)
ℏ4 q 2 (1 + a2 q 2 )2

40
4m2 a4 β 2 4m2 a4 β 2
= = (2.216)
ℏ4 (1 + a2 q 2 )2
2
ℏ4 a12 + q 2 a4
dσ 4m2 β 2
= 2 (2.217)
dΩ ℏ4 a12 + q 2

tes
(b)
Z1 Z2 e2 2Ze2 β V0
For a coulomb potential, V (r) = r
. For Z1 = Z2 , V (r) = r
= r
= r
. This
implies that β = V0 = 2Ze2

θ
and q 2 = 4k 2 sin2 ( 2θ )

Also, q = 2k sin 2
From;

No
dσ 4m2 β 2
= 2
dΩ ℏ4 a12 + q 2

dσ dσ
= lim (2.218)
dΩ Rutherf ord a−→∞ dΩ Y akuwa
4m2 V02
= (2.219)
ℏ4 (q 2 )2
4m2 V02
= 2 (2.220)
ℏ4 4k 2 sin2 ( 2θ )
ure
16m2 Z 2 e4
= (2.221)
16ℏ4 k 4 sin4 ( 2θ )
m2 Z 2 e4
= (2.222)
ℏ4 k 4 sin4 ( 2θ )
ℏ2 k2
But E = 2m

m 2 Z 2 e4
= . 4 θ (2.223)
ℏ2 k 2 sin ( 2 )
ct

2 2
dσ Ze 1
= . 4 θ (2.224)
dΩ Rutherf ord 2E sin ( 2 )
Individual Assignment;
Read and make notes about Partial Wave Analysis
Le

41
2.4 Chapter Exercises
1. The Schrodinger equation of a particle confined to the positive x-axis is;

ℏ d2 ψ

tes
− + mgxψ = Eψ
2m dx2

with ψ(0) = 0, ψ(x) −→ 0 as x −→ ∞ and E is the energy eigen value. Use the
trial function xe−ax and obtain the best value of a
2
2. A particle of mass m moves in the attractive central potential V (r) = − g3 , where
r2
4 12 kr
k
e− 2 as the trial function,

No
g is a constant. Using the normalized function 8π
estimate the upper bound to the energy of the lowest state. Assume;

g2

ℏ 1 d 2 d
Ĥ = − r − 3
2m r2 dr dr r2
Also;

∞ √ ∞
Z r Z
−ax 1 x n −ax n!
xe dx = ; x e dx = if n is positive and a > 0
0 2a a 0 an+1

3. Evaluate the ground state energy of a harmonic oscillator of mass m and angular
ure
momentum ω using a trial function;
(
πx

cos 2a
, −a ≤ x ≤ a
ϕ(x) =
0 |x| > a

4. A particle of mass m is trapped in a potential well which has the form V = 12 mω 2 x2 .

Use the variational method with the normalized trial function √12 cos πx

2a
in the
limits −a < x < a to find the best value of a.
ct

5. Evaluate the first order correction to the energy of the n = 1 state of an oscillator
of mass m and angular frequency ω subjected to a potential

1 1
V (x) = mω 2 x2 + bx, bx << mω 2 x2
2 2
Le

6. Use the variational method for solving the Schrodinger equation for the truncated
harmonic oscillator potential;

1
V (x) = kx2 , f orx > 0
2

42
= ∞, f orx < 0

Use the trial function ψ = xe−bx where b is the variational parameter, to calculate
an approximate value for the ground state energy.

tes
7. A simple harmonic oscillator of mass m and angular frequency ω is perturbed by
an additional potential 12 bx2 . Obtain the first and second order corrections to the
ground state energy.

8. Calculate the first order energy shift of the first three states of a particle in a one
dimensional box problem (walls at x = 0 and x = a) due to the potential;
V1 x
(a)

No
a
x 2

(b)V1 a
, where V1 is a constant
(c) What is the condition under which the perturbation condition is valid?
(0)
9. Calculate the first order correction to E3 for a particle in a one dimensional box
with walls at x = 0 and x = L due to the following perturbations.
(i) Ĥ1 = 10−3 E1 Lx
x 2
(ii) Ĥ1 = 10−3 E1

L

(iii) Ĥ1 = 10−3 E1 sin x

ure
L

10. A particle which is initially (t = 0) in the ground state of an infinite one dimensional
potential box with walls at x = 0 and x = a is subjected for 0 ≤ t ≤ α to a
t
perturbation Ĥ1 (t) = x̂2 e− τ . Calculate to the first order, the probability of finding
the particle in its first excited state for t ≥ 0.
r !
n2 π 2 ℏ2 2 nπx
En = , ψn (x) = sin
2ma2 a a
ct

11. A particle initially( i.e. t −→ −∞ )in its ground state in an infinite potential well
whose walls are located at x = 0 and x = a is subjected at a time t = 0 to a time
2
dependent perturbation V̂ (t) = ϵx̂2 e−t where ϵ is a real number. Calculate to the
probability that the particle will be found in its first excited state after a sufficiently
Le

long time (t −→ ∞).

r !
n2 π 2 ℏ2 2 nπx
En = , ψn (x) = sin
2ma2 a a

43
12. A particle of mass m in the ground state of a one-dimensional harmonic oscillator is
t
placed in a perturbation V̂ (t) = −V0 x̂2 e− τ . Calculate to the first order probability
theory the probability of finding the particle in its first excited state after a long
time.

tes
13. Consider a one dimensional harmonic oscillator with angular frequency ω and elec-
tric charge e at a time t = 0 in the ground state. An electric field is applied for a
time t = τ so that the perturbation is;

Ĥ1 = −eE x̂, 0≤t≤τ

No
= 0, else where

where E is the electric field strength and x̂ is the position operator

(a) Use the first order perturbation theory to calculate the probability of tran-
sition to a state n = 1.
(b) Use the first order perturbation theory to calculate the probability of tran-
sition to a state n = 2.

14. Find the differential cross section in the first born approximation for neutron-
r
neutron scattering in the case where the potential is approximately V (r) = V0 e− a .
ure
r2
15. Consider the scattering from the potential V (r) = V0 e− a2 . Find
(a) the differential cross section in the first born approximation.
(b) the total cross section.

16. Calculate the born approximation differential cross section for the following poten-
tial (
V0 , r≤a
V (r) =
ct

0 r>a

17. Use the born approximation to calculate the differential cross section for scattering
by the central potential V (r) = rα2 where α is a constant
Z ∞
sin ax π
Le

Given dx = ; f or a>0
0 x 2

2V0 eαr
18. Using the born approximation approach for the potential V (r) = r

44
(a) Write down the expression for the scattering amplitude and show that;

4mV0
f (θ) =
ℏ2 (α2 + q 2 )

tes
Z ∞
αr q θ
Hint; e sin(qr)dr = and q = 2k sin
0 (α2 + q 2 ) 2

(b) Establish that the total cross section is;

32πm2 V02
σtotal =
α2 ℏ4 (α2 + 4k 2 )

No
19. With the aid of the born approximation, find the scattering amplitude f 9θ for the
truncated coulomb potential,

1 1
V (r) = c − r < a, and V (r) = 0 f or r ≥ a
a r

Find the expression for the scattering amplitude at very small angles of θ and hence
deduce the approximate value of sin 2θ at which the differential cross section has

fallen to one-third of its forward value.

2m ∞
Z
ure
T ake; f (θ) = − 2 rV (r) sin(qr)dr
ℏq 0
ct
Le

45
3 Angular Momentum

3.1 Orbital Angular Momentum

tes
⃗ = ⃗r × p⃗ ; where ⃗r
Classically, the orbital angular momentum of a particle is given by L
and p⃗ are the position vector and momentum of the particle, respectively.

Using the expressions for ⃗r and p⃗ in the Cartesian systems of coordinates;

⃗r = xî + y ĵ + z k̂ (3.1)

No
p⃗ = px î + py ĵ + pz k̂ (3.2)
⃗ is ;
the angular momentum L

î ĵ k̂
⃗ = x y z
L (3.3)
px p y pz

⃗ = î y z − ĵ x z + k̂ x y
L (3.4)
py pz px pz px p y
ure
= î (ypz − zpy ) − ĵ (xpz − zpx ) + k̂ (xpy − ypx ) (3.5)

= î (ypz − zpy ) + ĵ (zpx − xpz ) + k̂ (xpy − ypx ) (3.6)

But;
⃗ = Lx î + Ly ĵ + Lz k̂
L (3.7)

Comparing equations (3.6) and (3.7) gives;

Lx = (ypz − zpy )
ct

Ly = (zpx − xpz ) (3.8)

Lz = (xpy − ypx )

The corresponding quantum operators are obtained by the standard prescription; p̂x =
∂ ∂ ∂
−iℏ ∂x , p̂y = −iℏ ∂y and p̂z = −iℏ ∂z . Therefore;
Le

∂ ∂
L̂x = (ŷ p̂z − ẑ p̂y ) = −iℏ y ∂z − z ∂y
∂ ∂

L̂y = (ẑ p̂x − x̂p̂z ) = −iℏz ∂x − x ∂z
(3.9)
∂ ∂
L̂z = (x̂p̂y − ŷ p̂x ) = −iℏ x ∂y − y ∂x

46
⃗ˆ are each Hermitian
These individual components of the angular momentum operator L
⃗ˆ its self.
and so, correspondingly is the operator L

3.1.1 Commutation Relations of Angular Momentum Components

tes
Here, we are to compute the commutation relations involving these component operators
using the fundamental commutators;

[j, p̂k ] = iℏδjk , [j, k] = [p̂j , p̂k ] = 0, j, k = x, y, z (3.10)

and the following commutator properties;

No
[Â ± B̂, Ĉ] = [Â, B̂] ± [B̂, Ĉ] (3.11)

[Â, B̂ Ĉ] = B̂[Â, Ĉ] + [Â, B̂]Ĉ (3.12)

Where Â, B̂ and Ĉ are arbitrary operators.

Now, let us compute [L̂x , L̂y ]

[L̂x , L̂y ] = [ŷ p̂z − ẑ p̂y , ẑ p̂x − x̂p̂z ] (3.13)

ure
= [ŷ p̂z , ẑ p̂x ] − [ŷ p̂z , x̂p̂z ] − [ẑ p̂y , ẑ p̂x ] + [ẑ p̂y , x̂p̂z ] (3.14)

Now, let us compute for each commutator brackets in (3.14);

[ŷ p̂z , ẑ p̂x ] = ŷ[p̂z , ẑ p̂x ] + [ŷ, ẑ p̂x ]p̂z

= ŷẑ[p̂z , p̂x ] + ŷ[p̂z , ẑ]p̂x + ẑ[ŷ, p̂x ]p̂z + [ŷ, ẑ]p̂x p̂z

[ŷ p̂z , ẑ p̂x ] = −iℏŷ p̂x (3.15)

[ŷ p̂z , x̂p̂z ] = ŷ[p̂z , x̂p̂z ] + [ŷ, x̂p̂z ]p̂z

= ŷx̂[p̂z , p̂z ] + ŷ[p̂z , x̂]p̂z + x̂[ŷ, p̂z ]p̂z + [ŷ, x̂]p̂2x

[ŷ p̂z , x̂p̂z ] = 0 (3.16)

[ẑ p̂y , ẑ p̂x ] = ẑ[p̂y , ẑ p̂x ] + [ẑ, ẑ p̂x ]p̂y

= ẑ 2 [p̂y , p̂x ] + ẑ[p̂y , ẑ]p̂x + ẑ[ẑ, p̂x ]p̂y + [ẑ, ẑ]p̂x p̂y

[ẑ p̂y , ẑ p̂x ] = 0 (3.17)

[ẑ p̂y , x̂p̂z ] = ẑ[p̂y , x̂p̂z ] + [ẑ, x̂p̂z ]p̂y

47
= ẑ x̂[p̂y , p̂z ] + ẑ[p̂y , x̂]p̂z + x̂[ẑ, p̂z ]p̂y + [ẑ, x̂]p̂z p̂y

[ẑ p̂y , x̂p̂z ] = iℏx̂p̂y (3.18)

Substituting equations (3.15), (3.16), and (3.17) into equation (3.14) gives;

tes
[L̂x , L̂y ] = −iℏŷ p̂x + 0 + 0 + iℏx̂p̂y (3.19)

= iℏ (x̂p̂y − ŷ p̂x ) (3.20)

[L̂x , L̂y ] = iℏL̂z (3.21)

Similarly, we can show that;

No
[L̂y , L̂z ] = iℏL̂x (3.22)

[L̂z , L̂x ] = iℏL̂y (3.23)

The commutation relations in equations (3.21, 3.22, and 3.23) can be combined together
into a single vector equation.
⃗ˆ × L
L ⃗ˆ = iℏL
⃗ˆ (3.24)

Now, let us consider the operator corresponding to the square of the orbital angular
momentum;
L̂2 = L̂2x + L̂2y + L̂2z (3.25)
ure
⃗
and compute the commutators of L̂2 with the components of L.

[L̂2 , L̂x ] = [L̂2x + L̂2y + L̂2z , L̂x ] (3.26)

= [L̂2x , L̂x ] + [L̂2y , L̂x ] + [L̂2z , L̂x ]

= [L̂2y , L̂x ] + [L̂2z , L̂x ]

since [L̂2x , L̂x ] = 0

= L̂y [L̂y , L̂x ] + [L̂y , L̂x ]L̂y + L̂z [L̂z , L̂x ] + [L̂z , L̂x ]L̂z

= −iℏL̂y L̂z − iℏL̂z L̂y + iℏL̂z L̂y + iℏL̂y L̂z

[L̂2 , L̂x ] = 0 (3.27)

In a similar way, it can be shown that;

[L̂2 , L̂y ] = 0 (3.28)

48
[L̂2 , L̂z ] = 0 (3.29)

As a consequence, we can write;

⃗ˆ = 0
[L̂2 , L] (3.30)

tes
⃗ˆ we can find
Since L̂2 commutes with all the components of the angular momentum L,
⃗ˆ
simultaneous eigenstates of L̂2 and any one component of L.

3.1.2 Lowering and Raising Operators of L̂

Let us now introduce the ladder operator technique similar to the one we applied to solve
the harmonic oscillator problem. Let the operators be defined as;

No
Lowering Operator ; L̂− = L̂x − iL̂y (3.31)

Raising Operator ; L̂+ = L̂x + iL̂y (3.32)

Considering conjugates of these two operators;

†
L̂†− = L̂x − iL̂y = L̂+ (3.33)

†
L̂†+ = L̂x + iL̂y = L̂− (3.34)
ure
From the above equations we realize that these two operators are not Hermitian but
instead are mutually ad-joint. Manipulating equations (3.31) and (3.32) results into;

L̂+ + L̂−
L̂x = (3.35)
2

L̂+ − L̂−
L̂y = (3.36)
2i
ct

By using the standard commutation relations, we can go a head and compute the com-
mutator of L̂z and L̂±
[L̂z , L̂+ ] = [L̂z , L̂x + iL̂y ] (3.37)

= [L̂z , L̂x ] + i[L̂z , L̂y ]

= iℏL̂y + i(−i)ℏL̂x

= ℏ L̂x + iL̂y

[L̂z , L̂+ ] = ℏL̂+ (3.38)

49
Also,
[L̂z , L̂− ] = [L̂z , L̂x − iL̂y ] (3.39)

= [L̂z , L̂x ] − i[L̂z , L̂y ]

tes
= iℏL̂y − i(−i)ℏL̂x

= iℏL̂y − ℏL̂x = −ℏ L̂x − iL̂y

[L̂z , L̂− ] = −ℏL̂− (3.40)

Hence the Lowering and Raising operators don’t commute with L̂z . However, they com-
mute with L̂2 .

No
[L̂2 , L̂± ] = [L̂2x + L̂2y + L̂2z , L̂± ] (3.41)

= [L̂2x , L̂± ] + [L̂2y , L̂± ] + [L̂2z , L̂± ]

= [L̂2x , L̂x ± iL̂y ] + [L̂2y , L̂x ± iL̂y ] + [L̂2z , L̂x ± iL̂y ]

= ±i[L̂2x , L̂y ] + [L̂2y , L̂x ] + [L̂2z , L̂x ] ± i[L̂2z , L̂y ]

= ∓ℏ L̂x L̂z + L̂z L̂x − iℏ L̂y L̂z + L̂z L̂y + iℏ L̂y L̂z + L̂z L̂y ± ℏ L̂x L̂z + L̂z L̂x

[L̂2 , L̂± ] = 0 (3.42)

ure
3.1.3 Simultaneous Eigenstates/functions of L̂2 and L̂z

From equation (3.30), since L̂2 commutes with L̂z , these two operators have simultaneous
eigen functions.

Suppose that the simultaneous eigen states are given by |l, m⟩, we can write the eigenvalue
equations as;
L̂2 |l, m⟩ = l(l + 1)ℏ2 |l, m⟩ (3.43)
ct

L̂z |l, m⟩ = mℏ |l, m⟩ (3.44)

Where l(l + 1)ℏ2 and mℏ are eigenvalues of L̂2 and L̂z respectively.

Acting on L̂± on both sides of equation (3.43) gives;

L̂± L̂2 |l, m⟩ = L̂± l(l + 1)ℏ2 |l, m⟩

(3.45)

L̂± L̂2 |l, m⟩ = l(l + 1)ℏ2 L̂± |l, m⟩ (3.46)

50
From equation (3.42), L̂± L̂2 = L̂2 L̂± , therefore, equation (3.46) becomes;

L̂2 L̂± |l, m⟩ = l(l + 1)ℏ2 L̂± |l, m⟩ (3.47)

tes

L̂2 L̂± |l, m⟩ = l(l + 1)ℏ2 L̂± |l, m⟩ (3.48)

From equation (3.48) we realize that the action of the operator L̂± on the simultaneous
eigen state |l, m⟩ of L̂2 is to form a new eigen state L̂± |l, m⟩. Thus L̂± |l, m⟩ are also
eigen states of L̂2 with eigenvalues l(l + 1)ℏ2 .

Also, acting L̂± on both sides of equation (3.44) gives;

No

L̂± L̂z |l, m⟩ = L̂± (mℏ |l, m⟩) (3.49)

L̂± L̂z |l, m⟩ = mℏL̂± |l, m⟩ (3.50)

From equation (3.50), we obtain these two equations;

L̂+ L̂z |l, m⟩ = mℏL̂+ |l, m⟩ (3.51)

L̂− L̂z |l, m⟩ = mℏL̂− |l, m⟩ (3.52)

ure
From the commutation relation [L̂+ , L̂z ] = −ℏL̂+ ,

L̂+ L̂z = L̂z L̂+ − ℏL̂+ (3.53)

Substituting equation (3.53) into eqaution (3.51) gives;

L̂z L̂+ − ℏL̂+ |l, m⟩ = mℏL̂+ |l, m⟩ (3.54)
ct

L̂z L̂+ |l, m⟩ − ℏL̂+ |l, m⟩ = mℏL̂+ |l, m⟩ (3.55)

L̂z L̂+ |l, m⟩ = mℏL̂+ |l, m⟩ + ℏL̂+ |l, m⟩ (3.56)

L̂z L̂+ |l, m⟩ = (m + 1) ℏL̂+ |l, m⟩ (3.57)

L̂z L̂+ |l, m⟩ = (m + 1) ℏ L̂+ |l, m⟩ (3.58)
Le

We see that L̂+ |l, m⟩ is an eigen state of L̂z with corresponding eigenvalues (m + 1)ℏ.

51
From the commutation relation [L̂− , L̂z ] = ℏL̂− ,

L̂− L̂z = L̂z L̂− + ℏL̂− (3.59)

tes
Substituting equation (3.59) into equation (3.52) gives;

L̂z L̂− + ℏL̂− |l, m⟩ = mℏL̂− |l, m⟩ (3.60)

L̂z L̂− |l, m⟩ + ℏL̂− |l, m⟩ = mℏL̂− |l, m⟩ (3.61)

L̂z L̂− |l, m⟩ = mℏL̂− |l, m⟩ − ℏL̂− |l, m⟩ (3.62)

No
L̂z L̂− |l, m⟩ = (m − 1) ℏL̂− |l, m⟩ (3.63)

L̂z L̂− |l, m⟩ = (m − 1) ℏ L̂− |l, m⟩ (3.64)

We as well see that L̂− |l, m⟩ is an eigen state of L̂z with corresponding eigenvalues
(m − 1)ℏ.

Norm of L̂+ |l, m⟩ and L̂− |l, m⟩

The norm of L̂+ |l, m⟩ is;

ure
2 ∗
L̂+ |l, m⟩ = L̂+ |l, m⟩ L̂+ |l, m⟩ (3.65)

2
L̂+ |l, m⟩ = ⟨l, m| L̂†+ L̂+ |l, m⟩ = ⟨l, m| L̂− L̂+ |l, m⟩ (3.66)

But
L̂− L̂+ = L̂2 − L̂2z − ℏL̂z (3.67)

Substituting equation (3.67) into equation (3.66) gives;

2
L̂+ |l, m⟩ = ⟨l, m| L̂2 − L̂2z − ℏL̂z |l, m⟩ (3.68)

= ℏ2 l(l + 1) − m2 − m = (l(l + 1) − m(m + 1)) ℏ2

(3.69)
p
Le

L̂+ |l, m⟩ = ℏ (l(l + 1) − m(m + 1)) (3.70)

The norm of L̂− |l, m⟩ is;

2 ∗
L̂− |l, m⟩ = L̂− |l, m⟩ L̂− |l, m⟩ (3.71)

52
2
L̂− |l, m⟩ = ⟨l, m| L̂†− L̂− |l, m⟩ = ⟨l, m| L̂+ L̂− |l, m⟩ (3.72)

But
L̂+ L̂− = L̂2 − L̂2z + ℏL̂z (3.73)

tes
Substituting equation (3.73) into equation (3.72) gives;

2
L̂− |l, m⟩ = ⟨l, m| L̂2 − L̂2z + ℏL̂z |l, m⟩ (3.74)

= ℏ2 l(l + 1) − m2 + m = (l(l + 1) − m(m − 1)) ℏ2

(3.75)
p
L̂− |l, m⟩ = ℏ (l(l + 1) − m(m − 1)) (3.76)

Recall that the norm of |l, m − 1⟩ and L̂− |l, m⟩ is L hence from equations (3.70) and
(3.76)
p
L̂+ |l, m⟩ = ℏ (l(l + 1) − m(m + 1)) |l, m + 1⟩ (3.77)
p
L̂− |l, m⟩ = ℏ (l(l + 1) − m(m − 1)) |l, m − 1⟩ (3.78)
ure
Equations (3.77) and (3.78) give the normalised eigen functions/states resulting from the
action of the raising and the lowering operators respectively.Wherem = −l, −l +1, ....., l −
1, l for l = 0, 1, 2, ...
ct
Le

53
3.2 Spin
In addition to orbital angular momentum, some particles such as electrons possess an
intrinsic (spin) angular momentum which, unlike the orbital angular momentum has

tes
nothing to do with the spatial degrees of freedom i.e. spin angular momentum doesn’t
relate to a particle’s coordinates or momenta, nor are the eigen states of spin dependent
on the boundary conditions imposed in coordinate space.

The spin angular momentum (Ŝ) operator and its cartesian components are Hermitian.
The algebraic theory of spin is a carbon copy of that of the orbital angular momentum
discussed in subsection 3.1 hence satisfying the following commutation relations.

No
[Ŝx , Ŝy ] = iℏŜz (3.79)

[Ŝy , Ŝz ] = iℏŜx (3.80)

[Ŝz , Ŝx ] = iℏŜy (3.81)

Also,
Ŝ 2 = Ŝx2 + Ŝy2 + Ŝz2 (3.82)

As earlier obtained in subsection 3.1, the z-component of the spin angular momentum
ure
commutes with the operator Ŝ 2 i.e.;

[Ŝ 2 , Ŝz ] = 0 (3.83)

Analogy to the angular momentum of a particle which is characterized by two quantum

numbers i.e.the orbital quantum number l and the azimuthal number m, the spin angular
momentum is also characterized by two quantum numbers, the spin s and its projection
ms on the z-axiz (the direction of the magnetic field), where ms = −s, −s + 1, ...., s − 1, s.
ct

Therefore, Ŝ 2 and Ŝz have simultaneous eigen functions |s, ms ⟩ with the following eigen-
vale problems;
Ŝ 2 |s, ms ⟩ = s(s + 1)ℏ2 |s, ms ⟩ (3.84)
Le

Ŝz |s, ms ⟩ = ms ℏ |s, ms ⟩ (3.85)

In nature, every fundamental particle has a specific spin. Some particles have integer
spin s = 0, 1, 2, ... (πmesons have s = 0, photons have s = 1 and so on) and others have
half-odd-integer spins s = 12 , 23 , 52 , ... (electrons, protons, and neutons have spin 21 , the
deltas have spin 32 and so on).

54
Particles with half-odd-integer spins are called fermions (quarks, electrons, protons, neu-
trons, etc) and those with integer spins are called bosons (pions, photons, gravitons, etc).

tes
Similarly we have;
p
Ŝ± |s, ms ⟩ = ℏ s(s + 1) − ms (ms ± 1) |s, ms ± 1⟩ (3.86)

Where Ŝ± = Ŝx ± iŜy and

D E D E 1 D ⃗ˆ2 E D 2 E ℏ2
Ŝx2 Ŝy2 s(s + 1) − m2s

= = S − Ŝz = (3.87)

No
2 2
D E D E
Where Â denotes Â = ⟨s, ms | Â |s, ms ⟩.

The spin states form an orthonormal and complete basis;

D ′ ′
E
s , ms s, ms = δs′ s δm′s ms (3.88)

s
X
|s, ms ⟩ ⟨s, ms | = Iˆ (3.89)
ms =−s
ure
Where Iˆ is a unit matrix.

1
3.2.1 Spin 2
and Matrix Elements of Spin Angular Momentum Components

For a Particle with spin 12 , the quantum number ms takes on only two values; ms = ± 12 .
The particle can be found in either of the following two states;

1 1 1 1
|s, ms ⟩ = , and |s, ms ⟩ = , − (3.90)
2 2 2 2
ct

in the Ŝ 2 and Ŝz basis. There are two eigen states, meaning that the Hilbert space is two
dimensional. The eigen states of Ŝ 2 and Ŝz are given by;

2 1 1 3 1 1
Ŝ ,± = ℏ2 , ± (3.91)
2 2 4 2 2
Le

1 1 ℏ 1 1
Ŝz , ± =± ,± (3.92)
2 2 2 2 2
Let us now study the matrix representation of spin s = 12 .

55
The two dimensional Hilbert space implies that the matrix that act on this space is a
2 × 2 form. Therefore, the spin operators for an electron are a 2 × 2 matrix.

′ ′
Evoking a bra s , ms onto equation (3.85) gives;

tes
D ′ ′
D ′ ′ E
s , ms Ŝz |s, ms ⟩ = ms ℏ s , ms s, ms (3.93)

= ms ℏδs′ s δm′s ms (3.94)

! ! !!
1
1 0 2
0 0 0
=ℏ + (3.95)
0 1 0 0 0 − 21

No
!
ℏ 1 0
= (3.96)
2 0 −1

Hence, we can represent Ŝz within the basis {|s, ms ⟩} as Ŝz

!
ℏ 1 0
Ŝz = (3.97)
2 0 −1

′ ′
Multiplying equation (3.84) by s , ms gives;
ure
D ′ ′
D ′ ′ E
s , ms Ŝ 2 |s, ms ⟩ = s(s + 1)ℏ2 s , ms s, ms (3.98)

= s(s + 1)ℏ2 δs′ s δm′s ms (3.99)

!
3ℏ2 1 0
= (3.100)
4 0 1

Hence Ŝ 2 is represented within the basis {|s, ms ⟩} as;

!
ct

3ℏ2 1 0
Ŝ 2 = (3.101)
4 0 1

To obtain the matrix elements of the operator Ŝ+ , we use the expression in equation
′ ′
(3.86). Evoking a bra s , ms on equation (3.86) gives;
Le

D ′ ′ 1
D ′ ′ E
s , ms Ŝ+ |s, ms ⟩ = ℏ (s(s + 1) − ms (ms + 1)) 2 s , ms s, ms + 1 (3.102)

56
s can only take one value (s = 12 ) while ms = ± 21 , thus;

21 ! 12 !
1 3 1 3 0 0 1 3 1 1 0 1
Ŝ+ = ℏ . − +ℏ . + (3.103)
2 2 2 2 0 0 2 2 2 2 0 0

tes
!
0 1
Ŝ+ = ℏ (3.104)
0 0
1
Where the first and second terms in equation (3.103) corresponds to ms = 2
and ms = − 21
respectively.

Also, to obtain the matrix element of the operator Ŝ− we use the expression in equation

No
′ ′
(3.86) by evoking a bra s , ms on both sides of it which gives;
D ′ ′ 1
D ′ ′
E
s , ms Ŝ− |s, ms ⟩ = ℏ (s(s + 1) − ms (ms − 1)) 2 s , ms s, ms − 1 (3.105)

1
= ℏ (s(s + 1) − ms (ms − 1)) 2 δs′ s δm′s ms −1 (3.106)

In equation (3.106), we realize that δs′ s = I however, ms = ± 21 which leads to;

21 ! 12 !
1 3 1 1 0 0 1 3 1 3 0 0
Ŝ− = ℏ . − − +ℏ . + − (3.107)
ure
2 2 2 2 1 0 2 2 2 2 0 0
!
0 0
Ŝ− = ℏ (3.108)
1 0

1
Since Ŝx = 2
Ŝ+ + Ŝ− ,

" ! !#
1 0 1 0 0
Ŝx = ℏ +ℏ (3.109)
2 0 0 1 0
ct

!
ℏ 0 1
Ŝx = (3.110)
2 1 0

1
Also, Ŝy = 2i
Ŝ+ − Ŝ−
Le

" ! !#
1 0 1 0 0
Ŝy = ℏ −ℏ (3.111)
2i 0 0 1 0

57
!
ℏ 0 1
= (3.112)
2i −1 0
!
ℏ 0 −i
Ŝy = (3.113)

tes
2 i 0

⃗ˆ2 and Ŝz are expressed in terms of two element column matrices
The joint eigen vectors of S
known as spinors. !

1 1 1
χ+ = , = (3.114)
2 2 0
!
1 1 0
χ− = , − = (3.115)

No
2 2 1
Let us now verify that these eigen vectors form a complete basis;
1 ! !
2
X 1 1 0 1
, ms , ms = 0 1 + 1 0 (3.116)
2 2 1 0
ms =− 21

!
1 0
= (3.117)
0 1
ure
Also, orthonormal; !
1
1 1 1 1
, ,= 1 0 =1 (3.118)
2 2 2 2 0
!
1 1 1 1 0
,− ,− = 0 1 =1 (3.119)
2 2 2 2 1

1 1 1 1 1 1 1 1
, ,− = ,− , =0 (3.120)
2 2 2 2 2 2 2 2
ct
Le

58
3.2.2 Pauli Matrices

Since the matrix elements Ŝz , Ŝx and Ŝy in equations (3.97), (3.110) and (3.113) respec-
tively carry a factor ℏ2 , we observe that they can be generally written as;

tes
ℏ
Ŝj = σ̂j , j = x, y, z (3.121)
2

The matrices σj are referred to as Pauli matrices, given as;

!
0 1
σ̂x = (3.122)
1 0

No
!
0 −i
σ̂y = (3.123)
i 0
!
1 0
σ̂z = (3.124)
0 −1
These matrices satisfy the following properties;

ˆ
σ̂j2 = I, (j = x, y, z) (3.125)
ure
σ̂j σ̂k + σ̂k σ̂j = 0, (j ̸= k) (3.126)

Where Iˆ is a 2 × 2 matrix.
Also,
T rσ̂x = T rσ̂y = T rσ̂z = 0 (3.127)

and the determinants of these matrices are all equal to −1 i.e. detσ̂x = detσ̂y = detσ̂z =
−1
ct

σ̂j can be expressed in terms of Ŝj (j = x, y, z) as;

2 2 2
σ̂x = Ŝx , σ̂y = Ŝy , σ̂z = Ŝz , (3.128)
ℏ ℏ ℏ

The above give the following commutation relations;

[σ̂x , σ̂y ] = 2iσ̂z (3.129)

[σ̂y , σ̂z ] = 2iσ̂x (3.130)

[σ̂z , σ̂x ] = 2iσ̂z (3.131)

59
Also,
σ̂x2 + σ̂y2 + σ̂z2 = 3Iˆ (3.132)

3.2.3 Transitions between Eigen States of Ŝz

tes
Let us consider the action of the operators Ŝx and Ŝy on the eigen states of Ŝz ; ± 21

1 ℏ 1
Ŝx + = σ̂x + (3.133)
2 2 2
! !
ℏ 0 1 1
= (3.134)
2 1 0 0

No
!
ℏ 0 ℏ 1
= = − (3.135)
2 1 2 2

1 ℏ 1
Ŝx + = − (3.136)
2 2 2
Also,
1 ℏ 1
Ŝx − = σ̂x − (3.137)
2 2 2
! !
ℏ 0 1 0
= (3.138)
ure
2 1 0 1
!
ℏ 1 ℏ 1
= = + (3.139)
2 0 2 2

1 ℏ 1
Ŝx − = + (3.140)
2 2 2
For Ŝy + 12 ,
1 ℏ 1
Ŝy + = σ̂y + (3.141)
ct

2 2 2
! !
ℏ 0 −i 1
= (3.142)
2 i 0 0
!
ℏ 0
Le

= (3.143)
2 i

1 iℏ 1
Ŝy = − (3.144)
2 2 2

60
For Ŝy − 12 ,
1 ℏ 1
Ŝy − = σ̂y − (3.145)
2 2 2
! !
ℏ 0 −i 0

tes
= (3.146)
2 i 0 1
!
ℏ −i
= (3.147)
2 0

1 −iℏ 1
Ŝy − = + (3.148)
2 2 2
The results in equations (3.136) and (3.140) show the action of the x-component of the

No
spin angular momentum Ŝx on the eigen states of Ŝz is to make a transition between the
two states; This also applies to Ŝy as seen in equations (3.144) and (3.148)

3.2.4 Action of the Lowering and Raising Operators of Ŝ on the Eigen States
of Ŝz

The lowering and raising operators of the spin angular momentum operator Ŝ are defined
as;
Ŝ+ = Ŝx + iŜy (3.149)
ure
Ŝ− = Ŝx − iŜy (3.150)

Now, let us consider the action of Ŝ+ on the eigen state + 21 and − 12 .
1
1
Ŝ+ + = Ŝx + iŜy + (3.151)
2 2

1 1
= Ŝx + + iŜy + (3.152)
2 2
ct

ℏ 1 iℏ 1
= − + i. − (3.153)
2 2 2 2

ℏ 1 ℏ 1
= − − − (3.154)
2 2 2 2
Le

1
Ŝ+ + =0 (3.155)
2
Similarly,
1 1
Ŝ+ − = Ŝx + iŜy − (3.156)
2 2

61

1 1
= Ŝx − + iŜy − (3.157)
2 2

ℏ 1 −iℏ 1
= +i (3.158)
2 2 2 2

tes

ℏ 1 ℏ 1
= + (3.159)
2 2 2 2

1 1
Ŝ+ − =ℏ (3.160)
2 2
Following the same procedure, it can be shown that;

1 1

No
Ŝ− + =ℏ − (3.161)
2 2

1
Ŝ− − =0 (3.162)
2
We observe that the highest state that the system can ever find its self in is the state
+ 12 and thus, further action of the raising operator on it gives zero (0).

We therefore conclude that the only fruitful action of the lowering operator is to act
on + 12 to produce − 21 and the only meaningful action of the raising operator is to
ure
transform − 21 to + 21 . Hence, there are only two possible choices to take and are con-
ventionally been considered as ”spin-up” (f or + 21 ) and ”spin-down” (f or − 12 ).

3.3 Total Angular Momentum

The total angular momentum of a particle is given by the total sum of its orbital angular
momentum (L̂) and spin angular momentum (Ŝ).

Jˆ = L̂ + Ŝ (3.163)
ct

For an isolated system of n-particles, the total angular momentum operator is the sum
of the angular momentum operators of the individual particle.
n
X
Jˆ = Jˆi
Le

i=1

It is defined by its three components Jˆx ,Jˆy , and Jˆz , which satisfy the following commu-
tation relations;
[Jˆx , Jˆy ] = iℏJˆz (3.164)

62
[Jˆy , Jˆz ] = iℏJˆx (3.165)

[Jˆz , Jˆx ] = iℏJˆy (3.166)

or equivalently by;

tes
Jˆ × Jˆ = iℏJ⃗ (3.167)

Since Jˆx ,Jˆy , and Jˆz don’t commute, they can not be simultaneously diagonalized i.e. they
don’t posses common eigen states.

The square of the angular momentum gives;

ˆ
J⃗2 = Jˆx2 + Jˆy2 + Jˆz2

No
(3.168)

This is a scalar operator, hence it commutes with Jˆx ,Jˆy , and Jˆz .

ˆ
[J⃗2 , Jˆi ] = 0 (i = x, y, z) (3.169)

All the operators; Jˆx ,Jˆy , and Jˆz are Hermitian and hence their eigen values are real.

ˆ
From equation (3.169), J⃗2 and Jˆz commute; Hence, they have simultaneous eigen func-
tions/vectors |j, m⟩ with the following eigen value problems;
ure
Jˆ2 |j, m⟩ = j(j + 1)ℏ2 |j, m⟩ (3.170)

Jˆz |l, m⟩ = mℏ |j, m⟩ (m = −j, ... + j) (3.171)

With j an integer or half an odd integer.

ˆ
3.3.1 Lowering and Raising Operators of J⃗
ct

Let us introduce two operators Jˆ+ and Jˆ− given as;

Lowering Operator ; Jˆ− = Jˆx − iJˆy (3.172)

Raising Operator ; Jˆ+ = Jˆx + iJˆy (3.173)

These two operators are not Hermitian since;

Jˆ+† = Jˆx† + (−i)Jˆy† = Jˆx − iJˆy = Jˆ− (3.174)

63
Some properties of these operators in relation to Jˆz and Jˆ2 are;

[Jˆz , Jˆ+ ] = ℏJˆ+ (3.175)

tes
[Jˆz , Jˆ− ] = −ℏJˆ− (3.176)

[Jˆ2 , Jˆ+ ] = 0 (3.177)

[Jˆ2 , Jˆ− ] = 0 (3.178)

Let us prove the relation in (3.175)

[Jˆz , Jˆ+ ] = [Jˆz , Jˆx + iJˆy ] (3.179)

No
[Jˆz , Jˆ+ ] = [Jˆz , Jˆx ] + i[Jˆz , Jˆy ]

= iℏJˆx + i(−iℏJˆy )

= ℏ(Jˆx + iJˆy )

[Jˆz , Jˆ+ ] = ℏJˆ+ (3.180)

We can as well prove the other relations in (3.176), (3.177) and (3.178).
ure
Let us see the effect of Jˆ+ and Jˆ− on the eigen states of Jˆz and Jˆ2 ; i.e. |j, m⟩.

Acting Jˆ± on both sides of equation (3.170) gives;

J± J |j, m⟩ = Jˆ± j(j + 1)ℏ2 |j, m⟩
ˆ ˆ2

(3.181)

Jˆ± Jˆ2 |j, m⟩ = j(j + 1)ℏ2 Jˆ± |j, m⟩ (3.182)

From equations (3.177) and (3.178) Jˆ± Jˆ2 = Jˆ2 Jˆ± ; therefore, equation (3.182) becomes;
ct

Jˆ2 Jˆ± |j, m⟩ = j(j + 1)ℏ2 Jˆ± |j, m⟩ (3.183)

Jˆ2 Jˆ± |j, m⟩ = j(j + 1)ℏ2 Jˆ± |j, m⟩ (3.184)
Le

Hence the states Jˆ± |j, m⟩ are eigen states of Jˆz2 .

Acting Jˆ+ on both sides of equation (3.171) gives;

J+ Jz |l, m⟩ = Jˆ+ (mℏ |j, m⟩)
ˆ ˆ (3.185)

64
Jˆ+ Jˆz |l, m⟩ = mℏJˆ+ |j, m⟩ (3.186)

From equation (3.175), Jˆ+ Jˆz = Jˆz Jˆ+ − ℏJˆ+ . Therefore, equation (3.186) becomes;

Jˆz Jˆ+ − ℏJˆ+ |l, m⟩ = mℏJˆ+ |j, m⟩

tes
(3.187)

Jˆz Jˆ+ |l, m⟩ − ℏJˆ+ |l, m⟩ = mℏJˆ+ |j, m⟩ (3.188)

Jˆz Jˆ+ |l, m⟩ = ℏ(m + 1)Jˆ+ |j, m⟩ (3.189)

Jˆz Jˆ+ |l, m⟩ = (m + 1)ℏ Jˆ+ |j, m⟩ (3.190)

Equation (3.190) asserts that Jˆ+ |j, m⟩ is also an eigen function of Jˆz with the corre-

No
sponding eigenvalues (m + 1)ℏ. Hence Jˆ+ is a raising operator. It raises the eigenvalues
of Jˆz by one unit of ℏ.

Acting Jˆ− on both sides of equation (3.171) and making use of equation (3.176) yields;

Jˆz Jˆ− |l, m⟩ = (m − 1)ℏ Jˆ− |j, m⟩ (3.191)

Showing that Jˆ− |l, m⟩ is an eigen state of Jˆz with eigenvalues (m − 1)ℏ. Hence Jˆ− is a
lowering operator.
ure
3.4 Addition of Angular Momentum
ˆ ˆ
Consider two angular momenta J⃗1 and J⃗2 which belong to two different subspaces 1 and
ˆ ˆ
2. For J⃗1 and J⃗2 either referring to two distinct particles or two different properties of the
same particle.

ˆ ˆ ˆ
The total angular momentum J⃗2 can be expressed in terms of J⃗1 and J⃗2 as;
ct

ˆ ˆ ˆ
J⃗ = J⃗1 + J⃗2 (3.192)

ˆ ˆ
We assume that J⃗1 and J⃗2 are independent angular momenta, i.e. each satisfies the usual
angular momentum commutation relations.
Le

[Jˆnx , Jˆny ] = iℏJˆnz , ....etc, [Jˆn2 , Jˆni ], ...etc (3.193)

Where n = 1, 2 and i = x, y, z.

65
Also, any component of Jˆ1 commutes with any component of Jˆ2 ;

[Jˆ1i , Jˆ2k ] = 0, i, k = x, y, z (3.194)

tes
so that the two angular momenta are compatible.

Now, denoting the joint eigstates of Jˆ12 and Jˆ1z by |j1 m1 ⟩, we have;

Jˆ12 |j1 m1 ⟩ = j1 (j1 + 1)ℏ2 |j1 m1 ⟩ (3.195)

Jˆ1z |j1 m1 ⟩ = m1 ℏ |j1 m1 ⟩ (3.196)

No
Also, denoting the joint eigstates of Jˆ22 and Jˆ2z by |j2 m2 ⟩, we have;

Jˆ22 |j2 m2 ⟩ = j2 (j2 + 1)ℏ2 |j2 m2 ⟩ (3.197)

Jˆ2z |j2 m2 ⟩ = m2 ℏ |j2 m2 ⟩ (3.198)

The four operators Jˆ12 , Jˆ22 ,Jˆ1z and Jˆ2z form a complete set of commuting operators; they
can thus jointly be diagonalised by the same states.

Denoting their joint eigenstates by |j1 j2 ; m1 m2 ⟩, we can write them as direct products of
ure
|j1 m1 ⟩ and |j2 m2 ⟩
|j1 j2 ; m1 m2 ⟩ = |j1 m1 ⟩ |j2 m2 ⟩ (3.199)

Because the coordinates of Jˆ1 and Jˆ2 are independent, we can rewrite equations (3.195)
to (3.198) as;
Jˆ12 |j1 j2 ; m1 m2 ⟩ = j1 (j1 + 1)ℏ2 |j1 j2 ; m1 m2 ⟩ (3.200)

Jˆ1z |j1 j2 ; m1 m2 ⟩ = m1 ℏ |j1 j2 ; m1 m2 ⟩ (3.201)

Jˆ22 |j1 j2 ; m1 m2 ⟩ = j2 (j2 + 1)ℏ2 |j1 j2 ; m1 m2 ⟩ (3.202)

Jˆ2z |j1 j2 ; m1 m2 ⟩ = m2 ℏ |j1 j2 ; m1 m2 ⟩ (3.203)

The kets |j1 j2 ; m1 m2 ⟩ form a complete basis as shown below;

! !
X X X
|j1 j2 ; m1 m2 ⟩ ⟨j1 j2 ; m1 m2 | = |j1 m1 ⟩ ⟨j1 m1 | |j2 m2 ⟩ ⟨j2 m2 | (3.204)
m1 m2 m1 m2

66
and since {|j1 m1 ⟩} and {|j2 m2 ⟩} are complete, also the basis {|j1 j2 ; m1 m2 ⟩} is complete.

j1 j2
X X
|j1 j2 ; m1 m2 ⟩ ⟨j1 j2 ; m1 m2 | = 1 (3.205)

tes
m1 =−j1 m2 =−j2

and also orthonormal.

D ′ ′ ′ ′
E D ′ ′ ED ′ ′ E
j1 j2 ; m1 m2 j1 j2 ; m1 m2 = j1 m1 j1 m1 j2 m2 j2 m2 (3.206)

= δj ′ ,j1 δj ′ ,j2 δm′ ,m1 δm′ ,m2 (3.207)

1 2 1 2

The basis {|j1 j2 ; m1 m2 ⟩} clearly spans the total space which is made of subspaces 1 and

No
2. From equation (3.199), we see that the dimensions N of this space is equal to the
product of dimensions of two subspaces spanned by {|j1 m1 ⟩} and {|j2 m2 ⟩};

N = (2j1 + 1) × (2j2 + 1) (3.208)

Let us introduce the step operators Jˆ1± = Jˆ1x + iJˆ1y and Jˆ2± = Jˆ2x + iJˆ2y whose action
on |j1 j2 ; m1 m2 ⟩ gives;
1
Jˆ1± |j1 j2 ; m1 m2 ⟩ = ℏ ((j1 ∓ m1 )(j1 ± m1 + 1)) 2 |j1 j2 ; m1 ± 1, m2 ⟩ (3.209)
ure
1
Jˆ2± |j1 j2 ; m1 m2 ⟩ = ℏ ((j2 ∓ m2 )(j2 ± m2 + 1)) 2 |j1 j2 ; m1 , m2 ± 1⟩ (3.210)
ˆ ˆ
The problem of adding two angular momenta J⃗1 and J⃗2 consists of finding the eigenvalues
and eigenvectors of Jˆ2 and Jˆz in terms of the eigenvalues and eigenvectors of Jˆ12 , Jˆ22 ,Jˆ1z
and Jˆ2z .

Considering the z-component of Jˆ

Jˆz = Jˆ1z + Jˆ2z (3.211)

Evoking a ket |j1 j2 ; m1 m2 ⟩ on equation (3.211) from the left,gives;

Jˆz |j1 j2 ; m1 m2 ⟩ = Jˆ1z + Jˆ2z |j1 j2 ; m1 m2 ⟩ (3.212)
Le

= Jˆ1z |j1 j2 ; m1 m2 ⟩ + Jˆ2z |j1 j2 ; m1 m2 ⟩ (3.213)

= ℏm1 |j1 j2 ; m1 m2 ⟩ + ℏm2 |j1 j2 ; m1 m2 ⟩ (3.214)

Jˆz |j1 j2 ; m1 m2 ⟩ = (m1 + m2 ) ℏ |j1 j2 ; m1 m2 ⟩ (3.215)

67
From (3.215) |j1 j2 ; m1 m2 ⟩ is also an eigenstate of Jˆz with corresponding eigenvalues
(m1 + m2 ) ℏ.

Now, let us consider the operation of Jˆ2 on the eigenstates |j1 j2 ; m1 m2 ⟩.

tes
From (3.192),
ˆ ˆ ˆ 2

J⃗2 = J⃗1 + J⃗2 (3.216)

ˆ ˆ ˆ ˆ
= J⃗12 + J⃗22 + 2J⃗1 .J⃗2 (3.217)
ˆ ˆ
Since all the components of J⃗1 commutes with all those of J⃗2 and since;

No
[Jˆ12 , Jˆ1 ] = [Jˆ22 , Jˆ2 ] = 0 (3.218)

It follows that Jˆ2 commutes with Jˆ12 and Jˆ22 .

Also,
ˆ ˆ
2J⃗1 .J⃗2 = Jˆ1+ Jˆ2− + Jˆ1− Jˆ2+ + 2Jˆ1z Jˆ2z (3.219)
ˆ
Applying the operator J⃗2 to the states |j1 j2 ; m1 m2 ⟩

ˆ ˆ ˆ ˆ ˆ
ure

J⃗2 |j1 j2 ; m1 m2 ⟩ = J⃗12 + J⃗22 + 2J⃗1 .J⃗2 |j1 j2 ; m1 m2 ⟩ (3.220)

ˆ ˆ ˆ

J⃗2 |j1 j2 ; m1 m2 ⟩ = J⃗12 + J⃗22 + Jˆ1+ Jˆ2− + Jˆ1− Jˆ2+ + 2Jˆ1z Jˆ2z |j1 j2 ; m1 m2 ⟩ (3.221)

Using expressions in (3.200)...(3.203), (3.209) and (3.210), equation (3.221) can be sim-
plified.

3.5 Chapter Exercises

1. Show that the operator L̂x is Hermitian

⃗ˆ = 0
2. Prove that [L̂2 , L]

3. Prove the following commutator relations;

(i) [x̂, L̂x ] = 0

(ii) [x̂, L̂y ] = iℏẑ
(iii) [x̂, L̂z ] = −iℏŷ
(iv) [p̂x , L̂y ] = iℏp̂z

68
4. Prove the following commutation relations
(i) [L̂+ , L̂− ] = 2ℏL̂z
(ii) [L̂z , L̂+ ] = ℏL̂+

tes
(iii) [L̂z , L̂− ] = −ℏL̂−

5. Show that;

1
(a) L̂2 = 2
L̂+ L̂− + L̂− L̂+

(b) L̂+ L̂− = L̂2 − L̂2z − ℏL̂z

6. Applying the operators L̂+ = L̂x + iL̂y and L̂− = L̂x − iL̂y on the eigenstates of L̂2

7. Show that [L̂2x , L̂2y ] = [L̂2y , L̂2z ] = [L̂2z , L̂2x ]

8. Evaluate;
(a) [L̂2 , p⃗ˆ]
(b) [L̂, p⃗ˆ2 ]
ure
⃗ˆ × L]
(c) [L̂, L ⃗ˆ

9. Assuming that a particle is in a state |l, m⟩, show that;

D E
(i) L̂x = 0
D E
(ii) L̂y = 0
D E D E
(iii) L̂2y = L̂2x = 21 [l(l + 1) − m2 ] ℏ2
ct

10. Calculate [L̂2x , L̂y ],[L̂2z , L̂y ] and [L̂2 , L̂y ], then show that ⟨l, m| L̂2x |l, m⟩ = ⟨l, m| L̂2y |l, m⟩.
h i
2 2 2 2
11. Show that L̂ , [L̂, x̂] = 2ℏ x̂L̂ + L̂ x̂ .
D E D E
12. Find L̂x and L̂y in the state |ψ⟩ = √13 (|1, 1⟩ + |1, 0⟩ + |1, −1⟩) where the first
Le

number in each ket denotes l and the second number denotes m.

1
13. Given that the !operators of the three
! components of spin ! of spin - 2 particle are Ŝx =
ℏ 0 1 0 −i 1 0
σ = ℏ2
2 x
, Ŝy = ℏ2 and Ŝz = ℏ2 , confirm the commutation
1 0 i 0 0 −1
relation of the components [Ŝx , Ŝy ] = iℏŜz , ...etc

69
14. Prove the following relations;
(a) Ŝ+ + 21 = 0
(b) Ŝ+ − 12 = ℏ
2
+ 12

tes
(c) Ŝ− + 21 = ℏ − 21
(d) Ŝ− − 12 = 0
ℏ2
(e) Ŝx2 = Ŝy2 = Ŝz2 = 4

(f) Ŝx Ŝy + Ŝy Ŝx = 0

15. Prove the following commutation relations involving Pauli matrices;

No
(i) [σ̂x , σ̂x ] = 2iσ̂z
(ii) [σ̂y , σ̂z ] = 2iσ̂x
(iii) [σ̂z , σ̂x ] = 2iσ̂y

16. Show that σ̂x2 = σ̂y2 = σ̂z2 = Iˆ

1
17. The matrix representation of spin - 2
system are given by the Pauli matrices;
! ! !
0 1 0 −i 1 0
σ̂x = ; σ̂y = ; σ̂z =
1 0 i 0 0 −1
ure
(a) Show that σ̂x σ̂y = iσ̂z , σ̂y σ̂z = iσ̂x and σ̂z σ̂x = iσ̂y
(b) Compute the commutation [σ̂x , σ̂y ]

18. Show that;

(i) Ŝx + 12 = ℏ
2
− 12
(ii) Ŝx − 12 = ℏ
2
+ 12
ct

(iii) Ŝy + 21 = iℏ
2
− 21
(iv) Ŝy − 12 = − iℏ2 + 21

19. Prove that the operators Ŝ+2 and Ŝ−2 are zero for the spin - 12 space.
Le

20. An electron is in the spin state

!
3i
χ=A
4

(a) Determine the normalization constant A

70
(b) Find the expectation values of Ŝx ,Ŝy and Ŝz
(c) Find the uncertainties ∆Ŝx , ∆Ŝy and ∆Ŝz .

21. The normalized spin wave function of an electron is given by;

tes
!
1 i
χ= √
5 2

(i) Find the expectation values of Ŝx ,Ŝy and Ŝz .

(ii) Find the uncertainties in the measurements of the observables Ŝx ,Ŝy and
Ŝz ,

No
h D E i
Hint; Ŝi = χ† Ŝi χ, i = x, y, z

22. What is the Hermitian adjoint of Jˆ+ Jˆ− ?

23. Prove the following commutation relations

(i) [Jˆ+ , Jˆ− ] = 2ℏJˆz
(ii) [Jˆz , Jˆ+ ] = ℏJˆ+
(iii) [Jˆz , Jˆ− ] = −ℏJˆ−
ure
24. Show that;

(a) Jˆ2 = 1
2
Jˆ+ Jˆ− + Jˆ− Jˆ+

(b) Jˆ+ Jˆ− = Jˆ2 − Jˆz2 − ℏJˆz

D E D E
(c) J = 3 Jˆx
ˆ 2

ˆ ˆ
25. Let the operators J⃗1 and J⃗2 be the respective angular momenta of the individual
ˆ ˆ ˆ
components of a two system. The total system has angular momentum J⃗ = J⃗1 + J⃗2 .
ct

Show that;
ˆ ⃗ˆ

(a) J1 .J2 = 2 J1+ J2− + J1− J2+ + Jˆ1z Jˆ2z
⃗ 1 ˆ ˆ ˆ ˆ

ˆ2 ⃗ˆ2 ˆ ˆ

ˆ2 ⃗ ˆ ˆ ˆ
(b) J = J1 + J2 + J1+ J2− + J1− J2+ + 2J1z J2z ˆ
Le

71
4 The Hydrogen Atom
The hydrogen atom involves two particles (the electron and the proton). The potential
energy of the electron in the electrostatic field of the proton is;

tes
e2 1 e2
V (r) = −k =− (4.1)
r 4πϵ0 r

were e is the electron charge and r is the distance of separation between the electron and
the proton.

Let ψ be the wave function that describes all the states of the electron around the nucleus

No
such that the three dimension Schrodinger equation for the system is;

ℏ2 2
− ∇ ψ + V (x, y, z)ψ = Eψ (4.2)
2µ

were ∇2 is the Laplacian operator, E is the total energy and µ is the reduced mass.

me M
µ= (4.3)
me + M

were me is the mass of the electron and M is the mass of the nucleus.
ure
Since the nucleus mass M is mach larger than the electron mass me , the reduced mass µ
is very close to the electron mass me .

We can now take advantage of symmetry and replace the Cartesian coordinates with the
spherical coordinates r, θ and ϕ, since the potential V (r) is a central potential i.e. it only
depends on distance not direction.
ct

Recall the transformation of cartesian coordinates to polar spherical coordinates as shown

in Figure 4.1.
Le

72
tes
No
Figure 4.1: Transformation of Cartesian Coordinates to Spherical

From triangle AOP in Figure 4.1, the side OA is simply the z-coordinate and can be
ure
obtained as;
OA
= cos θ, z = r cos θ (4.4)
OP
Similarly, from triangle AOP ,

AP
= sin θ, AP = OP cos θ, OQ = r sin θ (4.5)
OP

From triangle BOQ , the side OB is the x-coordinate and it can be obtained as;

OB
ct

= cos ϕ, OB = OQ cos ϕ (4.6)

This implies that;

x = r sin θ cos ϕ (4.7)
Le

Since the side BQ is equal to OC, BQ also represent the y-coordinate and it can be
obtained as;
BQ
= sin ϕ, BQ = OQ sin ϕ (4.8)
OQ
This implies that;
y = r sin θ sin ϕ (4.9)

73
Using equations (4.4), (4.7) and (4.9), equation (4.2) can be expressed in spherical polar
coordinates as;

ℏ2 1 ∂ ∂2

2 ∂ 1 ∂ ∂ 1
− r + 2 sin θ + 2 2 ψ + V (r)ψ = Eψ (4.10)

tes
2µ r2 ∂r ∂r r sin θ ∂θ ∂θ r sin θ ∂ϕ2

were ψ = ψ(r, θ, ϕ)

Thus, in spherical polar coordinates;

Ĥ(r, θϕ)ψ(r, θ, ϕ) = Eψ(r, θ, ϕ) (4.11)

No
Therefore, ψ(r, θ, ϕ) is an eigenfunction.

Equation (4.10) is separable and the plan is to look for a variable separable solution such
that;
ψ(r, θ, ϕ) = R(r)f (θ)g(ϕ) (4.12)

4.1 Solutions to the Schrodinger Equation by Separation of

Variables
ure
Substituting equation (4.12) into (4.10) gives;

1 ∂ 2∂ 1 ∂ ∂
r R(r)f (θ)g(ϕ) + 2 sin θ R(r)f (θ)g(ϕ)+
r2 ∂r ∂r r sin θ ∂θ ∂θ
(4.13)
1 ∂2 2µ
2 2 2
R(r)f (θ)g(ϕ) + 2 (E − V )R(r)f (θ)g(ϕ) = 0
r sin θ ∂ϕ ℏ

Substituting for V in equation (4.13) and multiplying through by r2 gives;

∂ 2 ∂ 1 ∂ ∂
r R(r)f (θ)g(ϕ) + sin θ R(r)f (θ)g(ϕ)+
∂r ∂r sin θ ∂θ ∂θ
(4.14)
1 ∂2 2µr2 e2

R(r)f (θ)g(ϕ) + 2 E+k R(r)f (θ)g(ϕ) = 0
sin2 θ ∂ϕ2 ℏ r

Let R(r)f (θ)g(ϕ) = Rf g, equation (4.14) becomes;

∂ 2 ∂ 1 ∂ ∂
r Rf g + sin θ Rf g+
∂r ∂r sin θ ∂θ ∂θ
(4.15)
1 ∂2 2µr2 e2

Rf g + 2 E+k Rf g = 0
sin2 θ ∂ϕ2 ℏ r

74
1 ∂ 2 g 2µr2 e2

∂ 2 ∂ 1 ∂ ∂f
fg r + Rg sin θ + 2 + 2 E+k Rf g = 0 (4.16)
∂r ∂r sin θ ∂θ ∂θ sin θ ∂ϕ2 ℏ r
Dividing equation (4.16) by Rf g gives

tes
1 ∂ 2 g 2µr2 e2

1 ∂ 2 ∂R 1 ∂ ∂f
r + sin θ + + 2 E+k =0 (4.17)
R ∂r ∂r f sin θ ∂θ ∂θ g sin2 θ ∂ϕ2 ℏ r

1 ∂ 2 g 2µr2 e2

1 ∂ 2 ∂R 1 ∂ ∂f
r + sin θ + + 2 E+k =0 (4.18)
R ∂r ∂r f sin θ ∂θ ∂θ g sin2 θ ∂ϕ2 ℏ r
2µr2 e2 1 ∂ 2g

1 ∂ 2 ∂R 1 ∂ ∂f
r + 2 E+k =− sin θ − (4.19)
R ∂r ∂r ℏ r f sin θ ∂θ ∂θ g sin2 θ ∂ϕ2

No
Equation (4.19) holds true if we equate both sides of it to a constant α

2µr2 e2

1 ∂ 2 ∂R
r + 2 E+k =α (4.20)
R ∂r ∂r ℏ r

1 ∂ 2g

1 ∂ ∂f
sin θ + = −α (4.21)
f sin θ ∂θ ∂θ g sin2 θ ∂ϕ2
Equation (4.20) contains only r variable and therefore, it is called a radial equation.
However, equation (4.21) still contains two variables and therefore further separation is
needed.
ure
Multiplying through equation (4.21) by sin2 θ gives;

1 ∂ 2g

sin θ ∂ ∂f
sin θ + = −α sin2 θ (4.22)
f ∂θ ∂θ g ∂ϕ2

1 ∂ 2g

sin θ ∂ ∂f
sin θ + α sin2 θ = − (4.23)
f ∂θ ∂θ g ∂ϕ2
Equation (4.23) holds true if we equate both sides of it to a constant m2l such that;
ct

sin θ ∂ ∂f
sin θ + α sin2 θ = m2l (4.24)
f ∂θ ∂θ

1 ∂ 2g
= −m2l (4.25)
g ∂ϕ2
Le

Let us call equation (4.24) are theta equation and equation (4.25) a phi equation.

75
4.1.1 Solutions of R(r), f (θ) and g(ϕ) Equations (Radial and Angular Eigen-
functions)

(a) The Solutions of g(ϕ)

tes
From equation (4.25),
∂ 2g
+ gm2l = 0 (4.26)
∂ϕ2
The general solution of such equation is

g(ϕ) = Aeiml ϕ (4.27)

No
were A represents the normalization constant, with ml = 0, ±1, ±2, .... The quantity ml
is called the magnetic quantum number.

(i) The boundary conditions for g(ϕ)

Replacing ϕ with ϕ + 2π, the position of the point under consideration should remain the
same i.e.
g(ϕ + 2π) = g(ϕ) (4.28)
ure
Therefore,
Aeiml (ϕ+2π) = Aeiml ϕ (4.29)

eiml (ϕ+2π) = eiml ϕ

eiml ϕ eiml 2π = eiml ϕ

ei2πml = eiml ϕ e−iml ϕ = 1

ei2πml = 1 (4.30)
ct

From Euler’s expansion, eix = cos x + i sin x. Using this, equation (4.30) takes the form

ei2πml = cos 2πml + i sin 2πml (4.31)

This relation holds true only when ml = 0, ±1, ±2, ±3....

76
(ii) The Normalization constant of g(ϕ)
Z 2π
g ∗ gdϕ = 1 (4.32)
0

tes
Z 2π
A 2
e−iml ϕ eiml ϕ dϕ = 1
0
Z 2π
2
A dϕ = 1
0

A2 (2π) = 1
r
1

No
A= (4.33)
2π
Therefore, equation (4.27) becomes;
r
1 iml ϕ
g(ϕ) = e (4.34)
2π

which is the complete solution of g(ϕ).

(b) The Solution of f (θ).

ure
From equation (4.24),

∂ ∂f
sin θ sin θ + αf sin2 θ − m2l f = 0 (4.35)
∂θ ∂θ

Dividing through equation (4.35) by sin2 θ gives;

m2l

1 ∂ ∂f
sin θ + αf − f =0 (4.36)
sin θ ∂θ ∂θ sin2 θ
ct

m2l

1 ∂ ∂f
sin θ + α− f =0 (4.37)
sin θ ∂θ ∂θ sin2 θ
∂y
Let y = cos θ, such that sin2 θ = (1 − y 2 ) and ∂θ
= − sin θ. Also,
Le

∂f ∂f ∂y
= (4.38)
∂θ ∂y ∂θ

∂f ∂f
= − sin θ (4.39)
∂θ ∂y

77
Multiplying both sides of equation (4.39) by sin θ gives;

∂f ∂f
sin θ = − sin2 θ (4.40)
∂θ ∂y

tes
∂f ∂f
sin θ = − 1 − y2 (4.41)
∂θ ∂y
Substituting equation (4.39) and (4.41) into equation (4.37) gives;

m2l

1 ∂f 2 ∂f

− sin θ − 1−y + α− f =0 (4.42)
sin θ ∂y ∂y 1 − y2

m2l

∂f ∂f

No
2
1−y + α− f =0 (4.43)
∂y ∂y 1 − y2
Equation (4.43) is a Legendre’s polynomial and it has physical significance only in the
range of y = +1 to y = −1.

Therefore, considering the one more form of f function so that this condition is satisfied
gives;
ml
f (θ) = 1 − y 2 2 Y (y) (4.44)

were Y is a function depending on variable y.

ure
Differentiating equation (4.44) with respect to y gives;

∂f ml ml dY
= −ml y(1 − y 2 ) 2 −1 Y + 1 − y 2 2 (4.45)
∂y dy
∂
Multiplying equation (4.45) by (1 − y 2 ) and ∂y
gives;

∂ ∂f2 ∂ m
2 2l 2 2 +1 dY
ml
1−y = −ml y(1 − y ) Y + 1 − y (4.46)
ct

∂y ∂y ∂y dy
h
2
ml m2l −1 i h m2l i ′
= −ml y(1 − y ) 2 + m2l y 2 1−y 2
Y − 2y(ml + 1) 1 − y 2
Y +
h m i
l +1 ′′ (4.47)
1 − y2 2 Y
Le

Substituting equation (4.44) and (4.47) into equation (4.43) gives;

h
2
ml m2l −1 i h m2l i ′
= −ml y(1 − y ) 2 + m2l y 2 1−y 2
Y − 2y(ml + 1) 1 − y Y + 2

h ml +1 i ′′

m2l

ml (4.48)
1 − y2 2 Y + α− 1 − y 2 2
Y =0
1 − y2

78
ml
Dividing through equation (4.48) by (1 − y 2 ) 2
gives;
′′ ′
1 − y 2 Y + 2(ml + 1)yY + [α − ml (ml + 1)] Y = 0 (4.49)

tes
′′ ′
1 − y 2 Y + 2βyY + λY = 0 (4.50)

were β = (ml + 1) and λ = [α − ml (ml + 1)].

Assuming that the function Y can be expressed as a power series expansion;

Y = a0 + a1 y + a2 y 2 + a3 y 3 + ... (4.51)

No
Such that;
′
Y = a1 + 2a2 y + 3a3 y 2 + 4a4 y 3 + ... (4.52)
′′
Y = 2a2 + 6a3 y + 12a4 y 2 + 20a5 y 3 + ... (4.53)

Substituting equations (4.51), (4.52) and (4.53) into equation (4.50) gives;

1 − y2 2a2 + 6a3 y + 12a4 y 2 + 20a5 y 3 + 2βy a1 + 2a2 y + 3a3 y 2 + 4a4 y 3 +

(4.54)
λ a0 + a1 y + a2 y 2 + a3 y 3 = 0

ure
(2a2 + λa0 ) + [6a3 + (λ − 2β) a1 ] y + [12a4 + (λ − 2β − 2) a2 ] y 2 = 0 (4.55)

The above equation is satisfied only if each term on the left hand side is individually
equal to zero ie., the coefficients vanish.

The general expression for the coefficients follow the condition below;

(n + 1)(n + 2)an+2 + [λ − 2nβ − n(n − 1)] an = 0 (4.56)

For n = 0, 1, 2, 3, ......
2nβ + n(n − 1) − λ
an+2 = an (4.57)
(n + 1)(n + 2)
Substituting the values of β and λ in equation (4.57) gives
Le

an+2 (n + ml )(n + ml + 1) − α
= (4.58)
an (n + 1)(n + 2)

This is a recursion formula for coefficient powers.

In order to obtain a valid wave function, the power series must contain a finite number of

79
terms number of terms which is only possible if the numerator in equation (4.58) becomes
zero.
(n + ml )(n + ml + 1) − α = 0 (4.59)

tes
α = (n + ml )(n + ml + 1) (4.60)

Since n and ml are both whole numbers, their sum must also be a whole number. Let
(n + ml ) = l such that;
α = l(l + 1) (4.61)

were l = 0, 1, 1, 2, ..... is the orbital quantum number.

No
Putting the value of α into equation (4.43) we get;

m2l

∂f ∂f 2
1−y + l(l + 1) − f =0 (4.62)
∂y ∂y 1 − y2

The general solution of equation (4.62) is;

f = Bpm ml
l (y) = Bpl (cos θ)
l
(4.63)

were B is the normalization constant and pm l (y) is the associated Legendre function
l
ure
defined as;
ml dml p (y)
l
pm
l
l
(y) = (1 − y) 2
m
(4.64)
dy l
were pl (y) is the Legendre polynomial given by;

1 dl (y 2 − 1)l
pl (y) = (4.65)
2l l! dy l

(i) Orthogonality of associated Legendre’s function.

It follows the condition;

Z +1
pm ml
k (y)pl (y) = 0
l
if k ̸= l (4.66)
−1
Le

Z +1
2 (l + ml )!
pml ml
k (y)pl (y) = if k = l (4.67)
−1 2l + 1 (l − ml )!
(ii) Normalization of f .

80
Z +1
∗
fm l l fm ll
dθ = 1 (4.68)
−1
Z +1
2
pm ml

tes
B k (y)pl (y) = 1
l
(4.69)
−1

2 (l + ml )!
B2 =1 (4.70)
2l + 1 (l − ml )!
s
2l + 1 (l − ml )!
B= (4.71)
2 (l + ml )!
Substituting equation (4.71) into equation (4.63) gives;

No
s
2l + 1 (l − ml )! ml
fl,ml (θ) = Bpm
l (y) =
l
p (cos θ) (4.72)
2 (l + ml )! l

is the complete solution to f (θ).

(c) The Solutions of R(r)

From equation (4.20),

ure
2µr2 e2

∂ 2 ∂R
r + 2 E+k R = l(l + 1)R (4.73)
∂r ∂r ℏ r

Dividing through equation (4.73) by r2 gives;

e2

1 ∂ 2 ∂R 2µ l(l + 1)
r + 2 E+k R= R (4.74)
r2 ∂r ∂r ℏ r r2

1 2 ∂ 2R e2

∂R 2µ l(l + 1)
r + 2r + 2 E+k − R=0 (4.75)
ct

r2 ∂r2 ∂r ℏ r r2
∂ 2 R 2 ∂R 2µE 2µke2 l(l + 1)

+ + + 2 − R=0 (4.76)
∂r2 r ∂r ℏ2 ℏr r2
Assume that the electron moving around the nucleus is some how bound. i.e.
Le

2µE µke2
− = α2 and =λ (4.77)
ℏ2 ℏ2 α

Therefore, equation (4.76) becomes;

∂ 2 R 2 ∂R

2 2αλ l(l + 1)
+ + −α + − R=0 (4.78)
∂r2 r ∂r r r2

81
Let us now define a new variable ρ = 2αr such that

∂ρ
= 2α (4.79)
∂r

tes
It follows that;
∂R ∂R ∂ρ ∂R
= . = 2α (4.80)
∂r ∂ρ ∂r ∂ρ
Also,

∂ 2R

∂ ∂R ∂ ∂R ∂ ∂ρ ∂R ∂ρ ∂ ∂R
2
= = 2α = 2α = . 2α (4.81)
∂r ∂r ∂r ∂r ∂ρ ∂ρ ∂r ∂ρ ∂r ∂ρ ∂ρ

No
∂ 2R ∂ 2R

∂ ∂R
= 2α 2α = 4α2 2 (4.82)
∂r2 ∂ρ ∂ρ ∂ρ
Substituting equations (4.80), (4.82) into equation (4.78) gives;

2

R 2
2∂ ∂R 2 2αλ l(l + 1)
4α + (2ρ) + −α + − R=0 (4.83)
∂ρ2 r ∂ρ r r2

Dividing equation (4.83) by 4α2 gives;

∂ 2R

1 ∂R 1 λ l(l + 1)
+ + − + − R=0 (4.84)
ure
∂ρ2 αr ∂ρ 4 2αr 4α2 r2

Using ρ = αr, equation (4.84) becomes;

∂ 2 R 2 ∂R

1 λ l(l + 1)
+ + − + − R=0 (4.85)
∂ρ2 ρ ∂ρ 4 ρ ρ2

As ρ −→ ∞, the above equation takes the form

∂ 2R 1
− R=0 (4.86)
ct

∂ρ2 4

The general solutions to equation (4.86) are;

ρ
R(ρ) = e 2 (4.87)
Le

ρ
R(ρ) = e− 2 (4.88)
ρ
The function R(ρ) = e 2 ←→ ∞ as ρ ←→ ∞. Hence, it is not acceptable. Therefore,

ρ
R(ρ) = e− 2 (4.89)

82
The acceptable solution is only valid for large values of ρ. For this reason we have to
think of a pre exponential part to be part of this solution so that it is valid for all values
of ρ.

tes
By incorporating some ρ -dependent unknown function F (ρ), equation (4.89) becomes;

ρ
R(ρ) = F (ρ)e− 2 (4.90)

Differentiating equations (??) w.r.t ρ at first and second order and then substituting the
2
values of R(r), ∂R
∂ρ
and ∂∂ρR in equation (4.85)

No
∂ 2F

2 ∂F 1 λ l(l + 1)
+ −1 + − + − F =0 (4.91)
∂ρ2 ρ ∂ρ ρ ρ ρ2

Hence, the problem has been reduced to determining the solution of F which can be
assumed a;

F (ρ) = ρs G(ρ) (4.92)

were G(ρ) represents a power series expansion of ρ.

G(ρ) = a0 + a1 ρ + a2 ρ2 + a3 ρ3 + ....
ure
f or a0 ̸= 0 (4.93)

j=∞
X
G(ρ) = aj ρ j (4.94)
j=0

Differentiating equation (4.92) w.r.t ρ gives;

′ ′
F (ρ) = sρs−1 G + ρs G (4.95)
ct

The second derivative of the same gives;

′′ ′ ′′
F (ρ) = s(s − 1)ρs−2 G + 2sρs−1 G + ρs G (4.96)

Substituting equations (4.92), (4.95) and (4.96) into equation (4.91) gives;
Le

s−2 s−1 ′ s 2′′ ′
s(s − 1)ρ G + 2sρ G +ρ G + − 1 sρs−1 G + ρs G +
ρ
(4.97)
1 λ l(l + 1) s
− + − ρ G(ρ) = 0
ρ ρ ρ2

83
Multiplying through equation (4.97) by 4ρ2 we get;

2 s−2 2 s−1 ′ 2 s ′′ 2 2 ′
4ρ s(s − 1)ρ G + 8sρ ρ G + 4ρ ρ G + 4ρ − 1 sρs−1 G + 4ρ2 ρs G +
ρ
(4.98)

tes

2 1 λ l(l + 1) s
4ρ − + − ρ G(ρ) = 0
ρ ρ ρ2

After some steps, we get to;

4s(s − 1)ρs + 8sρs − 4sρs+1 − 4ρs+1 + 4λρs+1 − 4l(l + 1)ρs G+

s+1 ′ ′′
(4.99)
8sρ + 8ρs+1 − 4ρs+2 G + 4ρs+2 G = 0

No
Dividing through equation (4.99) by ρs gives;
′
[4s(s − 1) + 8s − 4sρ − 4ρ + 4λρ − 4l(l + 1)] G + 8sρ + 8ρ − 4ρ2 G +

′′
(4.100)
4ρ2 G = 0

If ρ = 0, the function G(ρ) = a0 and the above equation becomes;

[4s(s − 1) + 8s − 4l(l + 1)] a0 = 0 (4.101)

Since a0 ̸= 0,
ure
[4s(s − 1) + 8s − 4l(l + 1)] = 0 (4.102)

[s(s − 1) + 2s − l(l + 1)] = 0 (4.103)

s(s + 1) − l(l + 1) = 0 (4.104)

s(s + 1) = l(l + 1) (4.105)

This implies that;

s=l or s = −(l + 1) (4.106)
ct

Now, putting s = −(l + 1) in the function F (ρ) becomes 0al+10

at ρ = 0 which is infinite.
Hence, this is not an acceptable solution. We are left with the solution s = l.

Substituting s = l in equation (4.100) gives;

′
[4l(l − 1) + 8l − 4lρ − 4ρ + 4λρ − 4l(l + 1)] G + 8lρ + 8ρ − 4ρ2 G +

′′
(4.107)
4ρ2 G = 0
′ ′′
[−4lρ − 4ρ + 4λρ] G + 8lρ + 8ρ − 4ρ2 G + 4ρ2 G = 0

(4.108)

84
Dividing through equation (4.108) by 4ρ gives;

′ ′′
[−l − 1 + λ] G + [2l + 2 − ρ] G + ρG = 0 (4.109)

tes
Differentiating equation (4.94) at first and second order gives;
∞
′
X
G (ρ) = aj .j.ρj−1 (4.110)
j=0

∞
′′
X
G (ρ) = aj .j.(j − 1)ρj−2 (4.111)
j=0

No
Substituting equations (4.94), (4.110) and (4.111) into equation (4.109) gives;
∞
X ∞
X ∞
X
j j−1
[−l − 1 + λ] aj ρ + [2l + 2 − ρ] aj .j.ρ +ρ aj .j.(j − 1)ρj−2 = 0 (4.112)
j=0 j=0 j=0

The above equation holds true only if the coefficients of individual powers of ρ become
zero. Simplifying equation (4.112) for two summation terms aj and aj+1 we get;

[−l − 1 + λ] aj ρj + aj+1 ρj+1 + [2l + 2 − ρ] aj .j.ρj−1 + aj+1 .(j + 1)ρj +

(4.113)
ρ aj .j.(j − 1)ρj−2 + aj+1 .(j + 1).j.ρj−1

ure
−laj ρj − aj ρj + λaj ρj − laj+1 ρj+1 − aj+1 ρj+1 + λaj+1 ρj+1 + 2laj .j.ρj−1 +
2aj .j.ρj−1 − ρaj .j.ρj−1 + 2laj+1 .(j + 1)ρj + 2aj+1 .(j + 1)ρj − ρaj+1 .(j + 1)ρj + (4.114)
ρaj .j.(j − 1)ρj−2 + ρaj+1 .(j + 1).j.ρj−1

Putting coefficients of ρj equal to zero gives;

−laj − aj + λaj − aj j + 2laj−1 (j + 1) + 2aj+1 (j + 1) + aj+1 j = 0 (4.115)

[−l − 1 + λ − j] aj + [2l(j + 1) + 2(j + 1) + (j + 1)j] aj+1 = 0 (4.116)

[2l(j + 1) + 2(j + 1) + (j + 1)j] aj+1 = − [−l − 1 + λ − j] aj (4.117)

l+1−λ+j
aj+1 = aj (4.118)
Le

2l(j + 1) + 2(j + 1) + (j + 1)j

l+1−λ+j
aj+1 = aj (4.119)
(j + 1)(2l + j + 2)
Equation (4.119) is the recursion formula where j is an integer. This expression allows
one to determine the coefficients aj+1 in terms of aj which is arbitrary.

85
Since the series G(ρ) consists of finite number of terms, the function F (ρ) becomes finite
at very large values of j and consequently, the function R(ρ) will also become infinite if
the number of the terms is not limited to finite values.

tes
To break off the series to a finite number of terms, we equate the numerator in equation
(4.119) to zero.
l+1−λ+j =0 (4.120)

λ=l+1+j (4.121)

Let us define a new quantum number n at this stage such that;

No
λ=l+1+j =n (4.122)

Since l and j are integers, n = 1, 2, 3, 4, .... n is the principal quantum number.

Moreover, as n > l + 1, the largest value that l can take is n − 1. Hence, the values of l
has a domain ranging from 0 to n − 1.

Putting λ = n in equation (4.109) gives;

ure
′ ′′
[−l − 1 + n] G + [2l + 2 − ρ] G + ρG = 0 (4.123)

Let 2l + 1 = p and n + l = q such that equation (4.123) becomes;

′ ′′
[q − p] G + [p + 1 − ρ] G + ρG = 0 (4.124)

The solutions of the above equation is the associated laguerre polynomial multiplied by
a factor i.e.
ct

G(ρ) = CLpq (ρ) = CL2l+1

n+l (ρ) (4.125)

The constant C can be set as normalized constant and the associated laguerre polynomial
is;
n−l−1
2l+1
X (−1)j+1 [(n + 1)!]2 ρj
Le

Ln+l (ρ) = (4.126)

j=0
(n − l − 1 − j)!(2l + 1 + j)!j!

Substituting equation (4.92) into (4.90) gives the radial eigenfunction.

ρ
R(ρ) = ρs G(ρ)e− 2 (4.127)

86
Substituting equation (4.125) into equation (4.127) gives;

ρ
R(ρ) = Ce− 2 ρl Lpq (ρ) (4.128)

tes
Since s = l
n−l−1
− ρ2 l
X (−1)j+1 [(n + 1)!]2 ρj
Rn,l (ρ) = Ce ρ (4.129)
j=0
(n − l − 1 − j)!(2l + 1 + j)!j!

Is the radial solution (eigenfunction) and j is an integer.

(i) The Normalization Constant of the function R(r).

No
Let us put the squared integral over whole configuration space sd unity
Z ∞
2
Rn,l (r).r2 dr = 1 (4.130)
0

The r2 factor is introduced to convert the length dr into a volume around the center of
the nucleus.

But ρ = 2αr
1

−2µE 2
ure
ρ=2 r (4.131)
ℏ2
1
−8µE 2
= r (4.132)
ℏ2
were E is the kinetic energy of the electron.
21
2µe2

ρ= r (4.133)
n(4πϵ0 )ℏ2
ct

2
ρ= r (4.134)
na0
4πϵ0 ℏ2
where a0 = me2
is the Bohr radius.

From equation (4.134),

2
dρ = dr (4.135)
na0
This implies that;
na0
dr = dρ (4.136)
2

87
Substituting equation (4.128) and (4.136) into equation (4.130) gives;
Z ∞ 2 h na0 i2 na0
2
eρ ρ2l Lpq (ρ)

C dρ = 1 (4.137)
0 2 2

tes
h na i3 Z ∞ 2
2 0
eρ ρ2l Lpq (ρ) dρ = 1

C (4.138)
2 0
" #
h na i3 2n [(n + l)!]3
0
C2 =1 (4.139)
2 (n − l − 1)!
s 3
2 (n − l − 1)!
C= (4.140)
na0 2n [(n + l)!]3

No
The complete normalized radial eigenfunction for the hydrogen atom is;
s 3
2 (n − l − 1)! − ρ l p
Rn,l (ρ) = e 2 ρ Lq (ρ) (4.141)
na0 2n [(n + l)!]3

The first three normalized radial eigen functions of the hydrogen atom are;
32
1 − ar
R10 (r) = 2 e 0 (4.142)
a0
ure
3
1 2 r − r
R20 (r) = 2− e 2a0 (4.143)
2a0 a0
3
1 1 2 r − r
R20 (r) = √ e 2a0 (4.144)
3 2a0 a0
Figure 4.2 shows the graphs of these three radial functions. Note that only for the
s-states (l = 0) are the radial functions different from zero at r = 0. This is due to the
presence of the factor rl in the expression (4.141).
ct

Note. The ground state of hydrogen is designated as the 1s state where ′ 1′ indicates the
energy level (n = 1) and ′ s′ indicates the orbital angular momentum state (l = 0)
Le

88
tes
length is a0

(ii) The Energy eigenvalues

From λ = µke2
ℏ2 α
,
No
Figure 4.2: Radial eigen functions R10 (r), R20 (r) and R21 (r) for hydrogen atom. The unit of
ure
µ2 k 2 e4
λ2 = (4.145)
ℏ4 α2
−2µE
Substituting the value of α2 = ℏ2
in equation (4.145) gives;

µ2 k 2 e4 −ℏ2 µk 2 e4

2
λ = =− (4.146)
ℏ4 2µE 2Eℏ2

But λ = n. Therefore,
µk 2 e4
n2 = −
ct

(4.147)
2En ℏ2
2
µe4

1
En = 2 2 (4.148)
n ℏ 4πϵ0
µe4
En = (n = 1, 2, 3, ...) (4.149)
Le

32π 2 ϵ20 ℏ2 n2
This is the famous Bohr formula. Bohr could not quite anticipate the correct assignment
of angular momentum to the energy levels.

89
The complete normalized eigen functions for the hydrogen atom are;

ψnlml (r, θ, ϕ) = Rnl (r)fl (θ)gml (ϕ) (4.150)

tes
For,

n = 1, 2, 3, 4, ......
l = 0, 1, 2, ....(n − 1) (4.151)
ml = −l, −l + 1, ...., 0, ....l − 1, l

The complete eigen functions for the lowest few states of hydrogen are;

No
32
1 1 − ar
ψ100 =√ e 0 (4.152)
π a0
32
1 1 r − 2ar
ψ200 =√ 1− e 0 (4.153)
π 2a0 2a0
5
11 2 − 2ar
ψ210 =√ re 0 cos θ (4.154)
2a0
π
52
1 1 − r
ψ21±1 = √ re 2a0 sin θe±iϕ (4.155)
ure
8 π a0
Example 4.10

Calculate the most probable distance of the electron in the ground state of the hydrogen
atom. What is the radial probability density of that distance?
Sln.

The Radial probability density;

Pnl (r) = r2 |Rnl (r)|2 (4.156)

For the ground state;

32
1 − ar
R10 (r) = 2 e (4.157)
Le

0
a0
32 2
2 1 − ar
P10 (r) = r 2 e 0 (4.158)
a0
4 2 − a2r
= r e 0 (4.159)
a30

90
dP10 (r)
P10 (r) will be maximum when dr
=0

2 − 2r − 2r
− r2 e a0 + 2re a0 = 0 (4.160)
a0

tes
r = a0 (4.161)

This is the most probable distance. The maximum value of the radial probability density
is;
4 −2
.a
(P10 )max = 3 (a0 )2 .e a0 0 (4.162)
a0
4 −2
(P10 )max = e (4.163)
a0

No
Example 4.11

Calculate 1r for an electron in the ground state of an hydrogen atom and use the results
to calculate.

(a) the average potential energy.

(b) the average kinetic energy.

ure
Sln.
For the ground state,
32
1 − ar
R10 (r) = 2 e 0 (4.164)
a0
Therefore;
1 1
= ⟨R10 (r)| |R10 (r)⟩ (4.165)
r r
Z ∞
ct

1 1
= |R10 (r)|2 r2 . dr (4.166)
r 0 r
Z ∞
4 −2r
= 3 re a0 dr (4.167)
a0 0

1 1
= (4.168)
Le

r a0
(a)
−e2 −e2

1
⟨V (r)⟩ = =− (4.169)
4πϵ0 r 4πϵ0 r

91
−e2 1
= . (4.170)
4πϵ0 a0
−e2 me2

= . (4.171)
4πϵ0 4πϵ0 ℏ2

tes
2 2
m e
⟨V (r)⟩ = − 2 (4.172)
ℏ 4πϵ0
⟨V (r)⟩ = −mc2 α2 (4.173)

(b)
⟨T ⟩ = E − ⟨V (r)⟩ (4.174)
2 2 " 2 2 #

No
m e m e
=− 2 − − 2 (4.175)
2ℏ 4πϵ0 ℏ 4πϵ0
2
e2

m
= 2 (4.176)
2ℏ 4πϵ0
mc2 α2
⟨T ⟩ = (4.177)
2
Note that from the above, ⟨T ⟩ = − 12 ⟨V (r)⟩.

Example 2.12
ure
The ground state wave function for the hydrogen atom is

1 − r
ψ(r) = p 3 e a0
πa0

Calculate the probability of finding the electron at a distance.

(a) less tha a0 of the radius

a0
(b) between 2
and 2a0 from the nucleus.

Sln.
Le

(a)
Z a0
P1 = |ψ(r)|2 dτ, dτ = 4πr2 dr (4.178)
0

92
!2
Z a0
1 − ar
2

P1 = p e 4πr 0dr (4.179)
0 πa30
4 a0 2 − a2r
Z
= 3 r e 0 dr (4.180)

tes
a0 0
But;
a0 r2 a0 r2 a30
Z
2r
2 − a0
r e dr = − − − (4.181)
2 2 4
Taking the limit from 0 to a0 ;
a0
5a30 −2 a30
Z
2r
2 − a0
r e dr = − e + (4.182)
0 4 4

No
a30
1 − 5e−2

= (4.183)
4
a3 4
P1 = 0 3 1 − 5e−2 = 0.323

(4.184)
4 a0
(b) Z 2a0
4 − a2r
P2 = 3 r2 e 0 dr (4.185)
a0 a0
2

5
= e−1 − 13e−4 (4.186)
ure
2
P2 = 0.682 (4.187)

4.2 Quantum Numbers l, n and ml

The three quantum numbers obtained from solving equation (4.19) are;

n-principal quantum number (n = 1, 2, 3, ....... n > 0).

l-orbital angular momentum quantum number (l = 0, 1, 2, 3, ......(n − 1)) l < n.

ml magnetic quantum number (ml = −l, −l + 1, ..0..l − 1, l |ml ≤ l|)

4.2.1 Principal Quantum Numbers (n)

The principal quantum number (n) results from the solution of the radial wave function
R(r) in equation (4.73). It specifies the energy of the electron in the atom and the average
distance (r) between the electron and the nucleus.

93
13.6eV
En = − (4.188)
n2
2
n
r= 0.529Å (4.189)

tes
Z
It also represent the maximum number of electrons in an orbit as n2 . The principal takes
on integral values.
n = 1, 2, 3, ....... n>0 (4.190)

4.2.2 Angular Momentum/Azimuthal/Orbital Quantum Number (l)

The orbital quantum number l is associated with the R(r) and f (θ) parts of the wave

No
function f (r, θ, ϕ). It determines the number of sub shells or sub levels to which the elec-
tron belongs. It also specifies the shape of an orbital with a particular principal quantum
number.

The quantum number l is related to the magnitude of the orbital angular momentum L
by
p
L = l(l + 1)ℏ (4.191)

This quantum result disagrees with the elementary Bohr theory of the hydrogen atom
ure
p
where L = nℏ. This is obvious in the state l = 0, L = 0(1)ℏ. Based on these results,
we will have to discard Bohr’s semiclassical ’planetary’ model of electrons orbiting the
nucleus.

Usually, a letter code is used to identify l to avoid confusion with n

l: 0 1 2 3 4 5 ...(n − 1)
(4.192)
Letter : s p d f g h ...
ct

Atomic states are normally reflected to their n and l numbers. Thus, a state/sub shell with
n = 2 and l = 1 is called a 2p state/sub shell. Examples of other various atomic states/sub
shells are 1s(n = 1, l = 0), 2s(n = 2, l = 0), 4d(n = 4, l = 2) and 6g(n = 6, l = 4).
Le

A state/sub shell such as 2d is not possible because this refers to n = 2 and l = 2; our
boundary condition requires that n > l.

The value of l also has a slight effect on the energy of the sub shell. i.e. the energy of
the sub shell increases with l (s < p < d < f ).

94
4.2.3 Magnetic Quantum Number ml

The angle ϕ is a measure of the rotation about the z-axis. The solution to g(ϕ) in
equation (4.34) specifies that ml is an integer and relate to the z-component of the

tes
angular momentum L ⃗ by;
Lz = ml ℏ (4.193)

The value of ml varies from −l to l through zero and it specifies the orientation in space
of an orbital of a given energy and shape.

This number divides the sub shells into individual orbits which hold the electrons; there
are 2l + 1 orbitals in each sub shell. Thus, the s sub shell has only one orbital, the p sub

No
shell has three orbitals and so on.

4.3 The Spin Quantum Number (s) and the Pauli Exclusion
Principle
4.3.1 The Spin Quantum Number (s)

The spin quantum number s describes the intrinsic angular momentum of the electron
within the orbital and it gives the projection of the spin angular momentum along the
ure
specific axis.

The value of s is ± 12 which signifies the spin or rotation or direction of an electron on its
axis during motion.

4.3.2 The Pauli Exclusion Principle

The Pauli exclusion principle states that no two electrons in an atom can have the same
set of quantum numbers (n, l, ml , ms ).
ct

This means that no more than two electrons can occupy the same orbital and that two
electrons in the same orbital must have opposite spins.
Le

Because an electron spins, it creates a magnetic field which can be oriented in one or
two directions. For two electrons in the same orbital, the spins must be opposite to each
other; the spins are said to be paired. These substances are not attracted to magnets
and are said to diamagnetic. Atoms with more electrons that spin in one direction than
another contains unpaired electrons. These substances are weakly attracted to magnets

95
and are said to be paramagnetic.

The exclusion principle plays an important role in the structure of atoms. It has a direct
effect on the spatial distribution of fermions (all particles of half-integer spin).

tes
Read about electron configuration and the periodic table.

4.4 Spin-Orbit Coupling

Let us imagine an electron orbiting the nucleus in an hydrogen atom; From the electron’s
point of view, the proton is circulating around it as shown in Figure 4.3.

No
ure

Figure 4.3: Hydrogen atom, from the electron’s perspective

⃗ due to the
The single electron of the hydrogen atom can feel an internal magnetic field B
ct

proton. A careful examination of this effect shows that the spins of the electron and the
orbital angular momentum interact, an effect called the spin-orbital coupling .

The magnetic field B⃗ exerts a torque on the spinning electron, tending to align its mag-
netic moment (⃗µ) along the direction of the field.
Le

⃗ Hence the Hamiltonian of the system is given

The dipole potential energy V = −⃗µ.B.
by;
⃗
Ĥ = −⃗µ.B (4.194)

The electron in its rest frame sees the proton moving at a speed u in a circular path.

96
From classical electrodynamics, the magnetic field experienced by the electron is;

B ⃗ = − 1 p⃗ × E
⃗ = − 1 ⃗u × E ⃗ = 1 E ⃗ × p⃗ (4.195)
c me c me c

tes
⃗ is the electric field generated by the pro-
where p⃗ = m⃗u is the linear momentum and E
ton’s coulomb potential field.

For an hydrogen atom where an electron moves in a central potential of a nucleus V (r) =
−eϕ(r), the electric field is;

⃗ r) = −∇ϕ(r) = 1 ∇V (r) = 1 . ⃗r dV
E(⃗ (4.196)

No
e e r dr
e 2
But V (r) = − 4πϵ0r
e2

⃗ r) 1 . ⃗r
E(⃗ =
e
⃗r (4.197)
e r 4πϵ0 r2 4πϵ0 r3
Substituting equation (4.197) into (4.195) gives;

⃗ = 1
B
e
⃗r × p⃗ =
e ⃗
L (4.198)
me c 4πϵ0 r3 4πϵ0 me cr3

⃗ BY;
ure
The magnetic moment µ
⃗ of the electron is related to its spin S

e ⃗
µ
⃗= S (4.199)
me c

Substituting equations (4.198) and (4.199) into equation (4.194) gives;

e ⃗ e ⃗
Ĥ = S. L (4.200)
me c 4πϵ0 me cr3
ct

e2

1 ⃗L ⃗
Ĥ = S. (4.201)
4πϵ0 me c2 r3
2

This expression is obtained by considering the rest frame of the electron; actually, the
electron accelerates as it orbits around the nucleus. To correct this, let us make an
appropriate kinematic correction known as the Thomas precession by throwing in a factor
Le

of 12 such that equation (4.201) becomes;

e2

1 ⃗L ⃗
ĤSO = S. (4.202)
8πϵ0 me c2 r3
2

This is the spin-orbit interaction.

97
For quantum mechanics, we deal with operators, hence equation (4.202) becomes;

e2

1 ⃗ˆ L
⃗ˆ
ĤSO = S. (4.203)

tes
8πϵ0 m e c2 r 3
2

We can use the perturbation theory to calculate the contribution of spin -orbit interaction
in the hydrogen atom. The Hamiltonian of the system is;

p⃗ˆ2 e2 e2

Ĥ = −k + ⃗ˆ L
S. ⃗ˆ (4.204)
2me r 2 2
8πme c r 3

No
Ĥ = Ĥ0 + ĤSO (4.205)

where Ĥ0 is the unperturbed Hamiltonian and ĤSO is the perturbed Hamiltonian.

⃗ and
In the presence of spin-orbit coupling, the Hamiltonian no-longer commutes with L
⃗ so, the spin and orbital are not separately conserved.
S,

However, Ĥ0 commutes with L2 , S 2 and the total angular momentum J⃗ given by;

J⃗ = L
⃗ +S
⃗ (4.206)
ure
Hence, these quantities are conserved.

Considering the perturbation, the eigenstates of Lz and Sz are not good states to use but
the eigenstates of L2 , S 2 , J 2 and Jz are.

Now,
⃗ˆ L
⃗ˆ

2 ⃗ ⃗ ⃗ ⃗
J = L + S . L + S = L̂2 + Ŝ 2 + 2S. (4.207)
ct

Also,
⃗ˆ L
⃗ˆ = L. ⃗ˆ = 1 Jˆ2 − L̂2 − Ŝ 2
⃗ˆ S

S. (4.208)
2
⃗ˆ S,
Let |nljm⟩ be the eigenstates of L. ⃗ˆ their corresponding eigenvalues are;
Le

2
⃗ˆ S
⟨nljm| L. ⃗ˆ |nljm⟩ = ℏ [j(j + 1) − l(l + 1) − s(s + 1)] (4.209)
2

98
For s = 12 , equation (4.209) becomes;

ℏ2

ˆ ⃗ˆ
⃗ 3
⟨nljm| L.S |nljm⟩ = j(j + 1) − l(l + 1) − (4.210)
2 4

tes
The eigen values of Ĥ (4.205) are given to the first order correction by;

Enlj = En(0) + ⟨nljm| ĤSO |nljm⟩ (4.211)

13.6eV (0)
Enlj = − 2
+ ESO (4.212)
n
(0)
where − 13.6eV
n2
are the energy levels of hydrogen and ESO is the energy due to the spin-

No
orbit interaction.

e2 ℏ2

(0) 3 1
ESO = ⟨nljm| ĤSO |nljm⟩ = j(j + 1) − l(l + 1) − ⟨nl| |nl⟩ (4.213)
16πϵ0 m2e c2 4 r3
But,
1 2
⟨nl| |nl⟩ = 3 (4.214)
r 3 n l(l + 1)(2l + 1)a30
Substituting equation (4.214) into equation (4.213) gives;

e2 ℏ2

(0) 3 2
ESO = j(j + 1) − l(l + 1) − (4.215)
ure
2
16πϵ0 me c 2 4 n l(l + 1)(2l + 1)a30
3

e2 ℏ2 j(j + 1) − l(l + 1) − 34

(0)
ESO = (4.216)
8πϵ0 m2e c2 n3 l(l + 1)(2l + 1)a30
Using the fine structure constant.
e2
α= (4.217)
4πϵ0 ℏc
Equation (4.216) becomes;
ct

j(j + 1) − l(l + 1) − 34

(0) αℏ
ESO = (4.218)
2m2e c2 n3 l(l + 1)(2l + 1)a30

(0)
Expanding En in terms of α gives;
Le

e4 me
En(0) =− (4.219)
32π 2 ϵ20 n2 ℏ2

e2 e2

1 me
=− (4.220)
2 4πϵ0 ℏ 4πϵ0 ℏ n2

99
1 me
= − (αc) (αc) 2 (4.221)
2 n
α2 c2 me
En(0) = − (4.222)
2n2

tes
4πϵ0 ℏ2
From a0 = m e e2
,

1 4πϵ0 ℏ ℏ
a0 = ℏ= (4.223)
me e2 cαme
This implies that;
ℏ3
a30 = 3 3 3 (4.224)
c α me
Substituting equation (4.224) into equation (4.218) gives;

No
3
c3 α3 m3e j(j + 1) − l(l + 1) −

(0) αℏ 4
ESO = (4.225)
2m2e c2 ℏ3 n3 l(l + 1)(2l + 1)

α4 cme j(j + 1) − l(l + 1) − 43

(0)
ESO = (4.226)
2ℏ2 n3 l(l + 1)(2l + 1)
Squaring equation (4.222) gives

2 α4 c4 m2e
En(0) = (4.227)
4n4
ure
2
(0)
4 En n4
α4 = (4.228)
c4 m2e
Substituting equation (4.228) into (4.226) gives;
2
(0)
2n En
j(j + 1) − l(l + 1) − 43

(0)
ESO = (4.229)
c3 ℏ2 me l(l + 1)(2l + 1)
ct
Le

100
4.5 The Zeeman Effect
The zeeman effect is the splitting of atomic energy levels and consequently the associated
spectral lines when atoms are placed in an external magnetic field. This effect provides

tes
a strong experimental confirmation of the quantization of angular momentum and also
tells why ml is called the magnetic quantum number.

Depending on the strength of the external magnetic field, the zeeman effect manifests its
self differently in terms of the number of spectral lines into which the original spectral
line splits. For weak magnetic fields(B ≈ 0.8T or less), it is divided into two classes;
the Normal Zeeman effect and Anomalous Zeeman effect.

No
In the normal zeeman effect, the splitting of spectral lines is determined by the orbital
angular momentum alone.i.e. zero spin, while in the Anomalous zeeman effect, it cannot
be explained in terms of orbital angular momentum alone., i.e. the spin angular momen-
tum is included.

The generic nature of the anomalous zeeman effect let to the discovery of the spin angular
momentum.
ure
4.5.1 Anomalous Zeeman Effect

The interaction of the external magnetic field B ⃗ ext with the electrons orbital and spin
magnetic dipole moments; µ⃗ L and µ
⃗ S give rise to two energy terms;

⃗ ext
VL = −⃗µL .B (4.230)

⃗ ext
VS = −⃗µS .B (4.231)
ct

whose sum is called the Zeeman energy.

⃗ ext − µ
ĤZ = −⃗µL .B ⃗ ext
⃗ S .B (4.232)

The magnetic dipole moment associated with the electron’s spin is µ ⃗ while
⃗ S = − mee c S
⃗ Therefore, equation
Le

that associated with the electron’s orbital motion is µ⃗ L = − 2mee c L.

(4.232) becomes;
e ⃗ ⃗

⃗ ext
ĤZ = L + 2 S .B (4.233)
2me c

101
⃗ ext to be along the z-direction such that B
Considering B ⃗ ext = Bext ẑ, equation (4.233)
becomes;
eBext
ĤZ = L̂z + 2Ŝz (4.234)
2me c

tes
The Hamiltonian of the system when placed in the external magnetic field becomes;

eBext
Ĥ = Ĥ0 + Ĥf s + L̂z + 2Ŝz (4.235)
2me c

where Ĥf s is the fine structure Hamiltonian.

The nature of the zeeman splitting depends critically on the strength of the external mag-

No
netic field in comparison with the internal field (4.198) that give rise to the spin-orbit
coupling.

⃗ ext << B
If B ⃗ , the fine structure dominates and Ĥz can be treated as a small perturbation.

⃗ ext >> B,
If B ⃗ the zeeman effect dominates and the fine structure becomes the perturba-
tion.

4.5.2 Strong Zeeman Effect

ure
The effect of a strong external magnetic field on the hydrogen atom is called the Paschen-
Back effect. If B⃗ ext >> B,
⃗ the zeeman effect dominates and the fine structure becomes
the perturbation.

We take the ’unperturbed’ Hamiltonian to be (Ĥ + Ĥz ) and the perturbation to be Ĥf s .

Let us now compute the ’unperturbed’ energies.

Since Ĥ commutes with Ĥ0 (because Ĥ0 commutes with L̂z and Ŝz ), they can be diago-
nalized by a common set of states |nlml ms ⟩ such that;

Ĥ |nlml ms ⟩ = Enlml ms |nlml ms ⟩ (4.236)

Neglecting Ĥf s , equation (4.235) becomes;

eBext
Ĥ = Ĥ0 + L̂z + 2Ŝz (4.237)
2me c

102
Substituting equation (4.237) into (4.236) gives;

eBext
Ĥ0 + L̂z + 2Ŝz |nlml ms ⟩ = Enlml ms |nlml ms ⟩ (4.238)
2me c

No
eBext ℏ
Enlml ms = En(0) + (ml + 2ms ) (4.242)
2me c
13.6eV eBext ℏ
Enlml ms = − 2
+ (ml + 2ms ) (4.243)
n 2me c
13.6eV
Enlml ms = − + µB Bext (ml + 2ms ) (4.244)
n2
eℏ
where µB = 2m ec
is a constant known as Bohr Magneton. From (4.244) we see that the
(0)
energy levels En are shifted by the amount ∆E = µB Bext (ml + 2ms ). This is known as
the Paschen-Back shift,
ure
The states |nlml ms ⟩ are degenerate since the energy doesn’t depend on l.

For the strong field zeeman effect, the external magnetic field overpowers the the spin-
orbit interaction effect and decouples L ⃗ and S⃗ so that they press about Bext nearly
independently; thus, the projection of L ⃗ behave as if S
⃗ = 0 and the effect reduces to
three lines, each of which is a closely spaced doublet.
ct
Le

103
4.6 Chapter Exercises
1. From x = r sin θ cos ϕ, y = r sin θ sin ϕ and z = rcosθ. Find the expression for r, θ
and ϕ.

tes
2. Find the spherical coordinates of the point (x, y, z) = (−1, 1, 2) in the Cartesian
coordinate system.

3. Calculate the cartesian coordinates of point whose spherical coordinates are (r, θ, ϕ) =
√
( 6, 450 , 1350 )

4. After separating the schrodinger equation using ψ = R(r)f (θ)g(ϕ), the equation

No
for ϕ is
1 d2 g
= k2
g dϕ2
where k is a constant. Solve for g(ϕ) in this equation and apply the appropriate
boundary conditions. Show that k must be 0 or positive or negative (k = ml , the
magnetic quantum number).

5. Obtain the time-independent Schrodinger equation in spherical polar coordinates

for a particle in a spherically symmetric potential. Carry out the separation of
variables and solve the angular equation.
ure
6. For the following cases, calculate the value of r at which the radial probability
density of the hydrogen atom reaches its maximum;
(a) n = 1, l = 0, m = 0
(b) n = 2, l = 1, m = 0

7. Using the fact that the radial momentum operator is given by p̂r = −iℏ 1r ∂r ∂
r.
Calculate the commutator [r̂, p̂r ] between the position operator r̂ and the radial
ct

momentum operator.

8. Find the expected value of r and r2 in the ground state of the hydrogen atom.

9. Consider a hydrogen atom which is in its ground state; the ground stste wave
function is given by;
Le

1 − r
ψ(r, θ, ϕ) = p 3 e a0
πa0
where a0 is the Bohr radius
(a) Find the most probable distance between the electron and the proton when
the hydrogen atom is in its ground state.

104
(b) Find the average distance between the electron and the proton.

10. An electron in the coulomb field of a proton is in a state described by the wave
function;

tes
3
α 2 − α2 r 2
ψ(r) = √ e 2
π
What is the probability that it will be found in the ground state of the hydrogen
atom.

11. Show that the magnetic moment of an orbital electron is given by;

e ⃗
⃗ =−
µ L

No
2me

where all symbols have their usual meaning.

12. Calculate to first order perturbation theory the contributions due to the spin-orbit
interaction for an hygrogen-like ion having Z protons.

13. What is meant by Zeeman effect?. Discuss in details how it is expalined using the
quantum theory.

14. Distinguish between the normal and anomalous Zeeman effect. Discuss the theory
ure
of the anomalous Zeeman effect.
ct
Le

105
5 Introduction to Two Level Systems

5.1 Matrix Form of the Schrodinger Equation in a Basis of Fi-

tes
nite Dimensions
From the Schrodinger equation;

∂ |ψ⟩
iℏ = Ĥ |ψ⟩ (5.1)
∂t

Replacing the partial time derivatives by the total time derivatives in equation (5.1) gives;

No
d |ψ⟩
iℏ = Ĥ |ψ⟩ (5.2)
dt

This is true, since we are only interested in the matrix representation of this equation
where Ĥ is a matrix, not a differential operator.

Let |j⟩ be our base states such that multiplying equation (5.2) from the left with ⟨j|
gives;
d X
iℏ ⟨j|ψ⟩ = ⟨j| Ĥ |ψ⟩ = ⟨j| Ĥ |i⟩ ⟨i|ψ⟩ (5.3)
dt i
ure
Let cj = ⟨i|ψ⟩ such that equation (5.3) becomes;

d X
iℏ cj = Hji cj (5.4)
dt i

where Hji = ⟨j| Ĥ |i⟩ Equation (5.4) is a matrix equation with c a column matrix and
H a square matrix; Therefore, this is the finite matrix represenation of the Schrodinger
equation.
ct

5.2 Two-Base States of a System

Considering the case where the system has only two states that form a complete set, the
Schrodinger equation (5.4) becomes;
Le

d
iℏ c1 = H11 c1 + H12 c2 (5.5)
dt

d
iℏ c2 = H21 c1 + H22 c2 (5.6)
dt

106
which can also be written as;
! ! !
d c1 H11 H12 c1
iℏ = (5.7)
dt c2 H21 H22 c2

tes
The two state schrodinger equation help us to understand some important basic physics
regarding the ammonia molecule.

Suppose that the off diagonal matrix elements H12 = H21 = 0, equation (5.7) gets
decoupled and it becomes;
dc1
iℏ = H11 c1 (5.8)
dt

No
dc2
iℏ = H21 c2 (5.9)
dt
Integrating equations (5.8) and (5.9) gives;
iE1 t
c1 (t) = Ae− ℏ (5.10)
iE2 t
c1 (t) = Be− ℏ (5.11)

where A and B are constants to be determined.

ure
The energies E1 and E2 are the eigenvalues of H for the base states |1⟩ and |2⟩, respec-
tively.

The general solution of the schrodinger equation (5.2) is;

X
|ψ(t)⟩ = |i⟩ ⟨i|ψ(t)⟩ (5.12)
i
ct

X
= |i⟩ ci
i
X
= ci |i⟩
i

|ψ(t)⟩ = c1 |1⟩ + c2 |2⟩ (5.13)

Substituting equation (5.10) and (5.11) into equation (5.13) gives;

iE1 t iE2 t
|ψ(t)⟩ = Ae− ℏ |1⟩ + Ae− ℏ |2⟩ (5.14)

The amplitudes in equation (5.14) corresponds to stationary states i.e, the probabilities

107
are independent of time.

In order to obtain the eigen states of the system, we have to diagonalise the matrix
elements of H.

tes
5.3 The Ammonia Molecule
In the ammonia molecule, N H3 , the hydrogen atoms are symmetrically located in a plane,
and the lone nitrogen atom can lie either above or below the symmetry plane of the H ′ s
as shown in Figure 5.1

No
ure

Figure 5.1: Two equivalent geometric arrangements of the ammonia molecule

Let us introduce two kets;

|1⟩=|N above the plane⟩ and |2⟩=|N below the plane⟩ and construct the matrix rep-
Le

resentation of the Hamiltonian using these two states depicted in Figure 5.1 as basis
states.

108
5.3.1 Assumptions

1. We shall assume that the states |1⟩ and |2⟩ are the base states needed to calculate
the ground states (lowest energy states of the N H3 molecule)

tes
2. There are more complex possibilities such as rotation, vibrations and electronic
motions but they all require considerably more energy and we shall ignore them for
simplicity.

By symmetry, the energy of the system in the two configurations must be the same. If
E0 is this energy, then;
H11 = H22 = E0 (5.15)

No
As such, the matrix elements H12 and H21 represent the interaction that mixes the two
base states. Physically, although the nitrogen is strongly repelled from the symmetry
plane of the hydrogen atoms due to the steep potential barrier, there is still a small prob-
ability that nitrogen tunnels through this symmetry plane.

Therefore, whichever configuration the molecule is in initially, there is a probability that

it ends up in the other configuration. This means that the matrix element of H between
the two states can not be zero.
ure
Using the symmetry argument again, we assert that;

H12 = H21 (5.16)

For convenience, let us choose that interaction matrix element to be a negative number
say −A with A being a real number since H must be Hermitian. Therefore,

H12 = H21 = −A (5.17)

Thus, the energy matrix is parameterized in terms of two real quantities E0 and A.
From equation (5.7), ! ! !
d c1 E0 −A c1
iℏ = (5.18)
dt c2 −A E0 c2
Le

Therefore; !
E0 −A
H= (5.19)
−A E0

109
5.3.2 Diagonalizing the Energy Matrix H

To diagonalize the energy matrix (5.19), we need to first solve the secular equation;

tes
|H − λI| (5.20)

obtained by equating the secular determinant to zero.

In equation (5.20), λ is the eigenvalue and I is the identity matrix.

! !
E0 −A 1 0
−λ =0 (5.21)
−A E0 0 1

No
E0 − λ −A
=0 (5.22)
−A E0 − λ

(E0 − λ)2 − A2 = 0 (5.23)

(E0 − λ)2 = A2 (5.24)

λ = E0 ± A (5.25)

This gives the eigenvalues of H. Labeling the values with subscripts I and II gives;
ure
EI = E0 + A (5.26)

EII = E0 − A (5.27)

The Hamiltonian in equation (5.19) can be written in terms of the identity matrix I and
the pauli matrix σx as
H = E0 I − Aσx (5.28)
! !
ct

1 0 0 1
where I = and σx = The two terms in equation (5.28) commute.
0 1 1 0

Also, the first term is already a diagonalized matrix with constant entries E0 . We are
therefore required to diagonalize the second term and to do that, we should note that
this term has eigenvalues ±1 (eigenvalues of σx are ±1).
Le

Recall that; once diagonalized, the matrix has eigenvalues on its major diagonal. This
implies that equation (5.28) becomes;

H = E0 I − A(±)I (5.29)

110
H = (E0 ∓ A)I (5.30)

which is a diagonal matrix with elements;

tes
H11 = E0 − A (5.31)

H22 = E0 + A (5.32)

The diagonalization procedure described above suggests that both H and the Pauli ma-
trix σx have the same diagonalizing matrix.

The diagonalizing matrix U of the pauli matrix σx is;

No
! !
+ √12 √1
2
⟨I|1⟩ ⟨I|2⟩
U= = (5.33)
√1 − 12
√ ⟨II|1⟩ ⟨II|2⟩
2

It is left to the reader to prove the above

We can verify by direct multiplication that U given by equation (5.33) and H given by
equation (5.9), it is indeed the case that;
!
E0 − A 0
ure
U HU −1 = U HU † = (5.34)
0 E0 + A

Let us now write the new kets; |I⟩ and |II⟩ in terms of the old ones; |1⟩ and |2⟩. With
the use of the matrix elements of U . E.g;
X
|I⟩ = |i⟩ ⟨i|I⟩ (5.35)
i

= |1⟩ ⟨1|I⟩ + |2⟩ ⟨2|I⟩

= |1⟩ ⟨I|1⟩∗ + |2⟩ ⟨I|2⟩∗

1
|I⟩ = √ (|1⟩ + |2⟩) (5.36)
2
Also,
Le

X
|II⟩ = |i⟩ ⟨i|II⟩ (5.37)
i

= |1⟩ ⟨1|II⟩ + |2⟩ ⟨2|II⟩

= |1⟩ ⟨II|1⟩∗ + |2⟩ ⟨II|2⟩∗

111
1
|II⟩ = √ (|1⟩ − |2⟩) (5.38)
2
We can easily verify that the states |I⟩ and |II⟩ are an orthonormal set; they are our new
base states.

tes
The existence of tunneling between the states |1⟩ and |2⟩ splits the energy states of the
molecule into two states with different energies, one with energy E0 − A and the other
with energy E0 + A (see Figure 5.2).

No
Figure 5.2: The two energy levels of the ammonia molecule

Let us now proceed to find out how the new base states |I⟩ and |II⟩ relate to the sta-
tionary states of the problem.
ure
The amplitudes of a general state ψ which are also the probability of the system to be
found in the new base states are;

cI = ⟨I|ψ⟩
(5.39)
cII = ⟨II|ψ⟩

These two amplitudes satisfy the Schrodinger equation;

! ! !
d cI E0 − A 0 cI
ct

iℏ = (5.40)
dt cII 0 E0 + A cII

Equations in (5.40) can easily be integrated and solved to yield;

−i(E0 −A)t
cI = Ce ℏ (5.41)
Le

−i(E0 +A)t
cII = De ℏ (5.42)

Where C and D are constants of integration which are essentially normalization constants
of the eventual wave function.

112
It follows that the general solution |ψ⟩ can be expressed as a linear combination of these
two functions.
−i(E0 −A)t −i(E0 +A)t
|ψ⟩ = Ce ℏ |I⟩ + De ℏ |II⟩ (5.43)

tes
|ψ⟩ = C |ψI ⟩ + D |ψII ⟩ (5.44)

Where |ψI ⟩ and |ψII ⟩ are the stationary states of the system. We therefore conclude that
both bases yield the same form of solutions.

We conclude that because there is some chance that the nitrogen atom can flip from one
position to another, the energy of the molecule is not just E0 as we would expect but
there are two energy levels (E0 − A) and (E0 + A). Every one of the possible states of

No
the molecule splits into two levels, whatever energy it has. The splitting of the energy
levels of the ammonia molecule is strictly a quantum effect.

5.4 The Ammonia Maser

The splitting of the two originally degenerate states of the ammonia molecule has a prac-
tical application, the ammonia maser. The maser is a device used for the amplification of
the microwave radiation in a stimulated emission. Its operation is based on the properties
of the ammonia molecule discussed in section 5.3.
ure
The energy differences between the states |I⟩ and |II⟩ discussed in section 5.3 is such
that a photon is emitted in a quantum jump from the highest to the lowest energy state
in microwave range.

For the maser to operate, there should be away of getting ammonia molecules predom-
inantly populating the excited state. The conditions should also allow for their de-
excitation and eventually donating radiation to a cavity so that microwave energy can be
ct

built in it.

The first step involves the interaction of an ammonia molecule with a static electric field
and the second, its interaction with a time dependent electric field.
Le

113
5.4.1 Ammonia Molecule in an External Static Electric Field

In the ammonia molecule, the valence electrons have a slight preference for the nitrogen
(N) atoms over the hydrogen atoms (H). As a result, the valence electrons stay on average

tes
a little closer to the nitrogen atom. This causes an imbalance in the charge distribution
in the ammonia molecule leading to the creation of an electric dipole moment.

The created electric dipole moment is directed from the nitrogen atom towards the hy-
drogen atom plane.

When there is an external electric field, there is an additional contribution to the Hamil-

No
tonian resulting from the interaction of the dipole with the electric field.

The interaction term can be written as −⃗µ.⃗ε, where µ

⃗ is the electric dipole moment and
⃗ε is the static electric filed.

It is important to note that when the nitrogen flips over to the other side, i.e. from state
|1⟩ to state |2⟩, the electric dipole moment also flips over (Figure 5.3)
ct ure

Figure 5.3: The two base states of the ammonia molecule give rise to opposite interaction with
the static filed. These states have an electric dipole moment µ
⃗

Consequently, the dipole interaction adds with a different sign in the two states;
Le

−⃗µ.⃗ε = µε f or |1⟩ (5.45)

−⃗µ.⃗ε = −µε f or |2⟩ (5.46)

114
Since there is only a diagonal contribution to the energy matrix from the dipole interaction
term, we have the Hamiltonian in the |1⟩ − |2⟩ basis as;
! !
⟨1| Ĥ |1⟩ ⟨1| Ĥ |2⟩ E0 + µε −A

tes
Ĥ = = (5.47)
⟨2| Ĥ |2⟩ ⟨2| Ĥ |2⟩ −A E0 − µε
!
E0 + µε −A
Ĥ = (5.48)
−A E0 − µε
We assume that the external electric field is sufficiently weak that is doesn’t affect the
amplitude for the nitrogen atom to tunnel through the barrier.

No
The two states |1⟩ and |2⟩ are not stationary; there are non zero off-diagonal matrix
elements of Ĥ in this basis. The eigenvalues of (5.48) are determined by solving the
secular equation;
ˆ =0
|Ĥ − λI| (5.49)
! !
E0 + µε −A 1 0
−λ =0 (5.50)
−A E0 − µε 0 1

E0 + µε − λ −A
=0 (5.51)
−A E0 − µε − λ
ure
(E0 + µϵ − λ)(E0 − µε − λ) − A2 = 0 (5.52)

λ2 − 2E0 λ + E02 − µ2 ε2 − A2 = 0

(5.53)

Equation (5.53) can be solved using the Buldoza method since it is in the form ax2 +
bx + c = 0. From which; √
−b ± b2 − 4ac
x= (5.54)
2
Using equation (5.54),
ct

p
2E0 ± 4E02 − 4 (E02 − µ2 ε2 − A2 )
λ= (5.55)
2
p
2E0 ± 2 µ2 ε2 + A2
= (5.56)
Le

2
1
λ1 = E0 + µ2 ε2 + A2 2 (5.57)
1
λ2 = E0 − µ2 ε2 + A2 2 (5.58)

Let us call the stationary state |α⟩ and |β⟩; their energy eigenvalues Eα and Eβ are given

115
from the solutions above;
21
Eα = E0 + µ2 ε2 + A2
12 (5.59)
Eβ = E0 − µ2 ε2 + A2

tes
These two energies are plotted as a function of the electric strength ε in Figure ( 5.4)

No
ure
Figure 5.4: Energy Levels of Ammonia Molecule in an Electric Field

The curves in Figure 5.4 are hyperbolic; for large fields, the splitting becomes propor-
tional to ε as the curves approach their asymptotes; the splitting doesn’t depend on A
ct

all because the strong field inhibits tunneling.

For small fields, the effect of tunneling interaction, A dominates and their energies vary
with the electric field via a term ε2
Le

116
5.4.2 Effect of the Electric Field

Suppose a beam of ammonia molecules is passed through slits into a region of a strong
transverse electric filed as shown in Figure 5.5

tes
No
Figure 5.5: Separation of the two tates of an Ammonia beam by an Electric Field with a gradient
in a direction perpendicular to the beam

The electrodes to produce the field are shaped so that the electric field varies rapidly
across the beam. Then, the square of the electric field ε2 will have a large gradient per-
pendicular to the beam.
ure
Now, a molecule in state |α⟩ has an energy which increases with ε2 and therefore this part
of the beam will be deflected towards the region of lower ε2 in order to minimize its energy.

A molecule in a state |β⟩ will on the other hand be deflected towards the region of larger
ε2 since its energy decreases as ε2 increases. Therefore, molecules in the different states
will be deflected in opposite directions and can be separated.

The energy µϵ is always smaller than A. Therefore, the square root term in equation
ct

(5.59) can be approximated by

1 µ 2 ε2

A 1+ (5.60)
2 A2
So, the energy levels are, for practical purposes;
Le

µ 2 ε2
Eα = E0 + A +
2A (5.61)
µ 2 ε2
Eβ = E0 − A +
2A

117
These energies vary approximately linearly with ε2 . The force on the molecule is then;

µ2 ⃗
F⃗ = ∇ε (5.62)
2A

tes
Many molecules have energy in the electric filed which is proportional to ε2 . The coef-
ficient is the polarizability of the molecule. Ammonia has unusually high polarizability
because of the small value of A in the denominator. Thus, Ammonia molecules are
unusually sensitive to an electric field.

5.4.3 Ammonia Molecule in a Time-Varying Electric Field

No
In the Ammonia maser, the beam with molecules in the state |α⟩ is sent through a reso-
nant cavity with a time-varying electric field. ε = ε0 cos(ωt). See figure 5.6
ure

Figure 5.6: In the ammonia maser, molecules in a higher state |α⟩ get de-excited to the lower
state |β⟩, building up the electromagnetic energy inside a resonant cavity

By interacting with the time-varying electric field, the molecules surrender their excita-
ct

tion energy (Eα − Eβ ) to the cavity as they de-excite to the state |β⟩.

Energy builds up in the electromagnetic filed of the maser cavity due to resonant absorp-
tion or emission of electromagnetic energy. Molecular energy is converted into the energy
Le

of an external electric field.

Note; Before the beam enters the cavity, we have to use filters which separate the beam
so that only the upper states enters.

118
5.5 Magnetic Resonance
Consider the motion of a particle with just a spin degree of freedom in a magnetic field.
For example;

tes
• Protons placed in a magnetic field as in the phenomenon of Nuclear Magnetic
Resonance (NMR).

• An electron localized at a crystal lattice site.

In both examples, the particles interact with the external magnetic field by virtue of their
intrinsic magnetic moment arising from spin;

No
⃗ = qg S
M ⃗ (5.63)
2mc

where q is the charge and g is the gyromagnetic ratio of the particle. For a proton, q = e
while for an electron, q = −e.

To be specific, let us consider protons in an NMR situation. The Hamiltonian of the

interaction is given as;
Ĥ = −M⃗ .B
⃗ (5.64)
ure
⃗ is along the z-axis, the Hamiltonian is diagonal in the Sz basis, producing the
If the B
familiar splits between the states |+z⟩ and |−z⟩.

In the absence of the magnetic field, the spin up and spin down states of the proton are
degenerate. The field removes this degeneracy.

If B0 is the magnitude of the field along the z-axis, equation (5.64) becomes;
ct

ge geℏ
Ĥz = − Ŝz B0 = − B0 σ̂z = −µp B0 σ̂z (5.65)
2mp c 4mp c

geℏ
where mp is the proton mass, µp = 4mp c
and σ̂z is a Pauli matrix.

From equation (5.65), we can obtain the eigenvalues of Ĥz for the corresponding eigen-
Le

states;
Ĥz |+z⟩ = −µp B0 σ̂z |+z⟩ = −µp B0 |+z⟩ (5.66)

Ĥz |−z⟩ = −µp B0 σ̂z |−z⟩ = +µp B0 |−z⟩ (5.67)

The eigenvalues are −µp B0 and +µp B0 respectively. The states |+z⟩ and |−z⟩ are sta-

119
tionary states of the Hamiltonian.

From equations (5.66) and (5.67), there is a Zeeman splitting of the energy level.

tes
Figure 5.7: Energy diagram with zeeman splitting; The lower energy level; −µp B0 (state |+z⟩).

No
The upper energy level; +µp B0 (state |−z⟩).

From Figure 5.7, the energy separation/difference is

∆E = 2µp B0 = ℏω0 (5.68)

ℏω0 = 2µp B0 (5.69)

geB0
This is known as the resonance condition; for ω0 = 2mp c
.
ure
In matrix form, the Hamiltonian Ĥz is given as
! !
⟨+z| Ĥz |+z⟩ ⟨+z| Ĥz |−z⟩ −µp B0 0
Ĥz = = (5.70)
⟨−z| Ĥz |+z⟩ ⟨−z| Ĥz |−z⟩ 0 +µp B0

For Nuclear Magnetic Resonance, the field in the z-direction is static, but an additional
time varying field is applied along the x-direction (see Figure 5.8 )

Bx = B1 cos ωt (5.71)
ct

where ω is the angular frequency of the radio-frequency oscillator

From Figure 5.8, the z-field is produced by an iron core electromagnet between whose
poles faces is placed the sample of protons (water can also be used). The protons are
surrounded by a solenoid coil coupled to a tunable radio-frequency (RF) circuit; The
Le

solenoid can be oriented in such a fashion that the RF magnetic field is along the x-axis.

The Hamiltonian of interaction of the protons with the radio-frequency magnetic field is
given by;
Ĥx = −µp Bx σ̂x = −µp B1 cos ωtσ̂x (5.72)

120
tes
Figure 5.8: Experimental arrangement of NMR. There is a time-dependent magnetic field in

No
addition to a constant field in the z-direction and perpendicular to it.

The total Hamiltonian Ĥ becomes

Ĥ = Ĥz + Ĥx
(5.73)
= −µp B0 σ̂z − µp Bx σ̂x

Ĥ = −µp B0 σ̂z − µp B1 cos ωtσ̂x (5.74)

In matrix form, Ĥ becomes;

ure
!
−µp B0 −µp B1 cos(ωt)
Ĥ = (5.75)
−µp B1 cos(ωt) µp B0

We have used the z-basis as in equation (5.70).

From equation (5.74),

B1
Ĥ = −µp B0 σ̂z + cos(ωt)σ̂x (5.76)
B0
ct

But µp B0 = 12 ℏω0 from equation (5.69). Therefore, equation (5.76) becomes;

1 B1
Ĥ = − ℏω0 σ̂z + cos(ωt)σ̂x (5.77)
2 B0

Le

ℏ ω0 B1
= − ω0 σ̂z + cos(ωt)σ̂x (5.78)
2 B0
ℏ
Ĥ = − [ω0 σ̂z + ω1 cos(ωt)σ̂x ] (5.79)
2

ω0 B1 geB0 geB1
where ω1 = B0
= 2m pc
. B 1
B0
= 2m pc
.

121
The Hamiltonian is time dependent, this implies that the application of an oscillating
magnetic field transverse to the z-axis, can induce transitions between the states |+z⟩
and |−z⟩. This can be done properly by adjusting the frequency of the transverse mag-

tes
netic field (B1 ).

To determine how these states evolve in time, we return to the Schrodinger equation
(5.2). We are going to work in the z-basis and express |ψ(t)⟩ in this basis by;
!
a(t)
|ψ(t)⟩ = a(t) |+z⟩ + b(t) |−z⟩ = (5.80)
b(t)

No
!
1
With the initial state; |ψ(0)⟩ = Using the Schrodinger equation;
0

d |ψ(t)⟩
iℏ = Ĥ |ψ(t)⟩ (5.81)
dt

Substituting equation (5.79) and (5.80) into equation (5.81) gives;

! ! !
ȧ(t) ℏ ω0 ω1 cos ωt a(t)
iℏ = (5.82)
ure
ḃ(t) 2 ω1 cos ωt −ω0 b(t)

da(t) db(t)
Where ȧ(t) = dt
and ḃ(t) = dt
.

This coupled set of first order differential equations can not be solved exactly.

In practice, however, the transverse field B1 is significantly weaker than the field B0 in
the z-direction and therefore, the frequency ω1 is considerably smaller than ω0 . Using
ct

this fact, we can obtain an approximate solution to (5.82).

Note; If ω1 = 0, the solutions to equation (5.82) are ;

iω0
t
a(t) = a(0)e 2

(5.83)
Le

iω0
t
b(t) = b(0)e 2

This suggests that we can can try writing;

iω0
! !
t
a(t) c(t)e 2
= iω0
t
(5.84)
b(t) d(t)e 2

122
Where we expect that we have included the major part of the time dependence in the
exponentials.

Substituting equation (5.84) into (5.82) we get;

tes
! !
ċ(t) ω1 c(t)eiω0 t
i = cos ωt
˙
d(t) 2 d(t)e−iω0 t
! ! (5.85)
ei(ω0 +ω)t + ei(ω0 −ω)t d(t)

ċ(t) ω1
i =
˙ ei(ω−ω0 )t + e−i(ω0 +ω)t c(t)

d(t) 4

Unless ω is chosen to be very near to ω0 , both exponentials in the second line of (5.85) are

No
rapidly oscillating functions that when multiplied by a more slowly oscillating function
such as c(t) and d(t), whose time scale is set by ω1 will cause the right-hand side of (5.85)
to average to zero.

However, if ω is near ω0 , the terms oscillating at (ω0 + ω) can be neglected with respect to
those oscillating at (ω0 − ω), and these latter terms are now oscillating sufficiently slowly
that c(t) and d(t) vary with time.

For our case, we shall consider and solve the time dependence when ω = ω0 ; the resonant
ure
condition.

5.5.1 The Resonance Condition (ω = ω0 )

Setting ω = ω0 and neglecting the exponentials oscillating at 2ω0 , equation (5.85) becomes
! !
ċ(t) ω1 d(t)
i = (5.86)
˙
d(t) 4 c(t)
ct

From equation (5.86), we get;

iω1
ċ(t) = − d(t)
4 (5.87)
˙ = − iω1 c(t)
d(t)
4
Le

Differentiating equation (5.87) gives;

iω1 ˙
c̈(t) = −d(t)
4 (5.88)
¨ = − iω1 ċ(t)
d(t)
4

123
Using equation (5.87), equation (5.88) becomes;
ω 2
1
c̈(t) = −c(t)
4 (5.89)
¨ = − ω1 d(t)
2

tes
d(t)
4

The solutions are as follows;

ω ω
1 1
c(t) = A1 cos t + A2 sin t (5.90)
4 4
4i
d(t) = ċ(t)
ω1

No
4i ω1 ω
1 ω1 ω
1
d(t) = − A1 sin t + A2 cos t (5.91)
ω1 4 4 4 4
ω ω
1 1
d(t) = i −A1 sin t + A2 cos t (5.92)
4 4
Applying the boundary conditions; c(0) = 1 and d(0) = 1 gives A1 = 1 and A2 = 0.
Therefore, we have
ω
1
c(t) = cos t
4
ω (5.93)
1
d(t) = −i sin t
ure
4

Using the above equations, the solutions to a(t) and b(t) become;
! ω0 !
a(t) cos ω41 t ei 2 t
= ω0 (5.94)
b(t) −i sin ω41 t ei 2 t

Thus, the probability of finding the particle in the state |−z⟩ at a time t is given by;

P− (t) = |⟨−z|ψ(t)⟩|2 = b∗ (t)b(t) = d∗ (t)d(t)

(5.95)

ω1
P− (t) = sin2 ( t) (5.96)
4
Thus, the probability of finding the particle in the state |+z⟩ at a time t is given by;
Le

P+ (t) = |⟨+z|ψ(t)⟩|2 = a∗ (t)a(t) = c∗ (t)c(t) (5.97)

ω1
P+ (t) = cos2 (t) (5.98)
4
Note that these probabilities add up to one since these two states form a complete set
and the probability is conserved in time.

124
If a particle is initially in a state |−z⟩ and makes a transition to a state |−z⟩, the energy
of the spin system is reduced by E+ − E− = ℏω0 . Assuming ω0 > 0, this energy is added
to the electromagnetic energy of the oscillating field that is stimulating the transition.

tes
For 0 < t < ω2π1 , the probability of making a transition to the lower energy state grows
until b∗ (t)b(t) = 1 and a∗ (t)a(t) = 0. Then the particle is in the state |−z⟩.

For ω2π1 < t < ω4π1 , the probability of being in the lower energy state decreases and that
of being in the higher energy state grows as the system absorbs energy back from the
electromagnetic field. This cycle of emission and absorption continues indefinitely (see

No
Figure 5.9)
ure
Figure 5.9: The probabilities |⟨+z|ψ(t)⟩|2 (solid line) and |⟨−z|ψ(t)⟩|2 (dashed line) for a spin-
half particle that is in a state |+z⟩ at t = 0 when the time dependent magnetic field in the
x-direction is tuned to be resonant frequency.
ct
Le

125
5.6 Chapter Exercises
1. Write the two-state Hamiltonian matrix in a certain basis |1⟩, |2⟩ in a general form
as;

tes
!
H11 H12
H21 H22
Impose hermiticity of H
(a) Find the eigenstates and the unitary transformation that diagonalizes the
Hamiltonian
(b) Express the eigenstates in terms of the old base states

No
2. Find the eigenvalues and eigen vectors of aσ̂z + bσ̂x + cIˆ where a, b, and c are
constants. σ̂z , σ̂x are Pauli matrices and Iˆ is a 2 × 2 matrix. Hence find the
eigenstates |α⟩ and |β⟩ of the ammonia molecule in a state electric field ⃗ε.

3. Describe the action of the Ammonia Maser.

4. In a NMR experiment, a sample of water displays resonant absorption when the

frequency of the transverse magnetic field goes through the value 42.4M Hz. If
the parallel magnetic field (B0 ) is 10000gauss. What value of g for the proton is
obtained?
ure
5. In a Nuclear Magnetic Resonance (NMR) experiment, the g factor of the proton
is to be measured using a static field of 10000gauss and a radio-frequency field of
amplitude 0.01gauss. What will be the resonant frequency?
ct
Le

126
References
Goswami, R. (1997). Quantum Mechanics, (2nd Edition), Waveland Press, Inc. Long-
Grove, Illinios, USA.

tes
Griffiths, D., J., and Schroeter, D., F. (2018). Introduction to Quantum Mechanics,
(3rd Edition), Cambridge University Press, London, UK.

Liboff, R., L. (1980). Introductory Quantum Mechanics. Addison-Wesley Publishing

Company, USA.

No
Zettilli, N. (2009). Quantum Mechanics; Concepts and Applications, (2nd Edition), John
Willey and Sons, West Sussex, UK.
ct ure
Le

127

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