Physics Dep., Ph.D.

- Course
Education Col., Semester- I, Oct. 2010
Al-Mustansyriyah Uni. Prof. Dr. Hassan N. Al-Obaidi

Advanced Quantum Mechanics

Syllabus
Chapter One: Quick Revision of Quantum Mechanics Concepts and
Some Applications
1-1 Rules Of Quantum Mechanics
1-2 Free Particle in a 1DPB
1-3 Harmonic Oscillator
1-3-1 Classical Theory of L.H.O.
1-3-2 Quantum Theory of L.H.O.
1-4 Central Potentials
1-4-1 Spherical Harmonics
1-4-2 Angular Momentum
1-4-3 Particle in A potential Sphere
1-4-4 Hydrogen Like Atoms
1-5 Rigid Rotator
1-6 Selection Rules
1-7 Matrix representation
1-7-1 Angular Momentum
1-7-2 Spin Angular Momentum

Chapter Two: Correction Methods

2-1 Time Independent None Degenerate Perturbation Theory
2-1-1 Stark Effect On Simple Harmonic Oscillator
2-1-2 Particle in Slanted Box
2-1-3 An Harmonic Oscillator
2-1-4 Third Order Correction
 2-2 Time Independent Degenerate Perturbation Theory
2-2-1 Stark's Effect on Hydrogen Like Atoms
2-2-2 Zeeman Effect and Double Degenerate States
2-3 Variation Method
2-3-1 Hydrogen Atom
2-4 The WKB Method ( Approximation )

Chapter Three : Time Dependant Quantum Mechanics

3-1 Formal Theory
3-1-1 Schrödinger Picture
3-1-2 Heisenberg Picture
3-1-3 Interaction Picture
3-2 Time Dependant Perturbation Theory
3-2-1 Step Perturbation
3-2-3 Sinusoidal Perturbation
3-3 Two Level Approximation
3-4 Rabi Solutions
3-5 Multi Level System
3-6 Adiabatic Perturbation
3-7 Fermi's Golden Rule

Chapter Four: Related Topics

4-1 Motion of Charge Particle In EM field
4-2 Propagators and Feynman Path Integrals
4-3 Potentials and Gauge Transformation
4-4 Interlude
4-5 Electric Dipole Approximation
4-6 Radiation and Matter Interacting
4-7 Einstein A and B Coefficients
References:

1- A Text Book of Quantum Mechanics by Mathews and

Venkatesan.
2- Quantum Mechanics by Landau and Lifshits.
3- Theory and Application of Quantum Mechanics by Ammon
Yariv.
4- Quantum Mechanics: Fundamental Principle and Applications
by Dawson.
5- Quantum Mechanics by Schiff.
6- Quantum Theory by Bohm.
7- Quantum Mechanics- An Introduction by Greiner.
8- Modern Quantum Mechanics by Sakurai.
 Chapter One
Quick Revision of Quantum Mechanics Concepts and Some
Applications

For every one who need to explore quantum physics world, It

important to know the reasons that requiring to use such a physical-
mathematical tool. In other word, one have to answer questions like;
What is the QM?, Why?, …etc.

1-1 Rules of Quantum Mechanics

Rule-1:Wavefunction
Given the DeBroglie wave-particle duality it turns out that one may
mathematically express a particle like a wave using a "wave function"
usually denoted by (Ψ (r,t) ). Consequently, in Q.M. the dynamical state
of a particle (system) is described by this wave function which replace the
classical concept of a trajectory and contain all what can be known about
the particle (system). This wave function must be well behaved and hence
satisfies three important conditions namely :
i- Finite
ii- Continuity
iii- Singularity
Accordingly, due to the "probabilistic or Boher interpretation of
wave function" one can define the probability density to be the
probability per unit length of finding the particle at a point x. In three
dimension it may represent the probability of finding he particle per unit
volume:

Pd = Ψ* (x, y, z). Ψ(x, y, z) = Ψ(x, y, z) 2

Hence, the probability of finding the particle within the volume V is :

Pv =∫ x ∫ y ∫ z Ψ(x, y, z) 2 dxdydz

Pv = ∫ v Ψ(x, y, z) 2 dτ
If one extending the above integration over all of the system space , then
the finite condition requires the probability becomes certainty (unity). i.e .

Pt = Ψ(x, y, z) 2 dτ = 1
∫
a.s
This equation called the normalization condition. However, any function
satisfy this condition called normalized. Elsewhere it must be
normalizable .i.e:

N 2 ∫ Ψ(x, y, z) dτ =1
+∞ 2

−∞
N being the normalization constant.

Rule-2: Observables

In Q.M. every observable quantity A like position, velocity,

energy,…etc. is represent by a correspondence mathematical operator Â.
Accordingly, in order to measure the observable A it is necessary to solve
the Eigen value equation;

ÂΨ n = a n Ψ n

Where, a n are the possible results of the measurement that  doing and
Ψ n are possible states of the system which called Eigen functions. If
the system has state satisfying the Eigen value equation then the
measurement of A definitely yield to the number a n.

Notes
1) Depending on position and momentum operators x̂ = x and.
. p̂ x = -ih dx
d
respectively one often be able to set up a desire
correspondence equation such as TDSE and TIDSE. (Show that)
2) Operator  is said to be Hermitical when satisfying the relation:
+∞ +∞
* *
∫ Ψ n Â Ψ m dτ = ∫ Ψ m (Â Ψ n ) dτ
-∞ -∞

i- Eigen value corresponds to any Hermitical operator must be real

quantities. (Prove)
ii- Eigen functions corresponding to different eigen values are
always orthogonal. i.e
+∞
*
∫ Ψn Â Ψ m dτ = 0 n≠m
-∞

(Prove and explain these facts ).

iii- Hence, one can directly define the orthonormality condition as:

+∞
* 0 n≠m
∫ Ψn Â Ψ m dτ = δ nm =
1 n=m
-∞

3) The functions Ψ n form a complete set of functions which in their

terms any arbitrary function f(x) can be expand:

f(x) = ∑ anΨ n ⇒ Completeness or Superposition Principle

n

4) It can be directly realized that the total probability is conserved. i.e.

dPt /dt = o (Prove)

Due to that a system is said to be in a stationary state and has a wave

functions of the form Ψ n (x, t) = Ψ n (x) e-iEt/. h

5) The flow of probability density at a position x is given by the

probability current density:
v − ih ∗ v r
S= (ψ ∇ψ −ψ∇ψ ∗) (Prove)
2m

Which satisfy the continuity equation:

dPt v v
+ ∇.S = 0 (Prove)
dt
Rule-3: Expectation Value

If the system is in state φ which is not an eigen state of a such

observable, then it is not possible to say with certainty what measured
value will be found for A. Therefore, one has to use the average value Ā
which called in Q.M. expectation value of A. It is defined
mathematically as:
A =< A >= ∫ Φ ∗ ÂΦ dτ / ∫ Φ ∗Φ dτ

= ∫ Φ ∗ ÂΦ dτ for normalised Φ

The probability that the measurement will yield the value an is

defined by:
2
Pn = ∫ Ψ n∗Φ dτ / ∫ Φ∗Φ dτ
(Discuss)
2
∗
= ∫ Ψ n Φ dτ for normalised Φ

The integration in last two equations called overlap integral. ( Explain)

Notes:
1) Expectation value of an observable A is the sum of the possible eigen
2
values a n times the corresponding partial probability in that state | cn | .
i.e. n
〈 A〉 = ∑ c n a n (Prove)
n
2 2
2) One can easily prove that: Pn = c n and ∑ cn =1
n

Rule-4:Variance

When the function Ψ n are a set of complete eigen functions of a two

different operators  and B̂
. i.e.

ÂΨ n = a n Ψ n and B̂Ψ n = b n Ψ n

Then the observables A and B are said to be compatible and their
correspondence operators must be commute. i.e. [Â, B̂] = 0. This means
when a particle described by an eigen state wave function Ψ n , the
measurement of A and B will certainly yield to precise results a n and
. b n respectively.
However, when the operators  and B̂ are not commute, the values
of A and B can not be predicted simultaneously. Therefore, to
determine these observables one has to use the expectation value <A>
and <B>. Since expectation value is the average of the probability
distribution that governs the measured results. Then the spread of the
probability distribution, which called Variance may represented by the
root-mean-square deviation of the measured result, which defined by:

∆A = {〈(A − A)2 〉}1/2 , ∆B = {〈 (B − B )2 〉}1/2

Or
∆A = {〈 A 2 〉 − 〈 A〉 2 }1/2 , ∆B = {〈 B2 〉 − 〈 B〉 2}1/2 (Prove)

Rule-5: Uncertainty Principle

If two observables A and B do not commute, i.e. [Â, B̂] = Ĉ ,

then in a series of measurements of A and B for a system having any
wave function Ψ , ∆A.∆B ≥ | C 2 | . (prove it). A typical examples for
such a case are; ∆x.∆p x ≥ h / 2 , ∆E.∆t ≥ h , ∆ϕ .∆L ≥ h , (prove)

H.W) Evaluate; [x̂, p̂ x ]

Rule-6: Equation of Motion

In Q.M. the equation of motion can be realized directly from the well-
known Ehernfest's theorem:
& = i 〈 Ĥ, Â 〉
& =A
A [ ] (Prove)
h
As shown in the formula:
ˆ& = i Ĥ, Â
A [ ] (Prove)
h
Equation of motion announce that, an observable A is a constant of
motion (conserved) when its operator  being commute with the
Hamiltonian.

H.W) Show that:

i- The momentum p is conserved for a free particle.
p ∂V
ii- x& = x and p& x = −
m ∂x

Notes
1) Degeneracy in Q.M. refers to the case when there are more than
one eigen function correspond to the same eigen value. However,
the number of these eigen functions is called the degree of
degeneracy.
2) Some wave function have a property that they own an even or odd
symmetry with respect to the reflection in the coordinate around
the origin. This symmetrical property called Parity. In
mathematical form:
+ Ψ(− x)
Ψ(x) = [
− Ψ(− x)

H.W: Show that: R̂Ψ n (x) = ±rn Ψ n (-x)

1-2 Free Particle in a 1DPB

This application deals with a free particle moves at the following

potential distribution;
zero 0<x <a
V(x) = [
infinite elsewhere

One may realize that SE is the key by which one can explore
microscopic systems. So, SE
−h 2 ∂ 2
Hˆ ψ n = Enψ n { + V( x) }ψ n = E n ψ n
2m ∂x 2

for this system SE goes to be;

−h 2 d 2 d 2ψ n 2mE
ψ n = E n ψn + k 2ψ n = 0 where k 2 =
2m dx 2 dx 2
h2
The general solution is then given by;

Ψn ( x) = Ae ikx + Be − ikx

Using the boundary conditions Ψ (0) = 0 and Ψn (a ) = 0 one can

nπ n
easily find that A=-B and k = . Thus, one may deduce the energies
and the wave functions to be; a
π 2h2 Ψn ( x) = N sin( naπ x)
En = n2 and ( Prove that)
2
2ma

H.W
1) Try to analyze the case when the potential beings zero along the
−a a
interval ≤ x ≤ and infinite elsewhere.
2 2
2) For the above investigated one, show that energies and their
correspondence wave functions may given in 3D by;

2 2
h 2 n x n y n z2 and 8 nπ nπ nπ
E= ( + + ) Ψn (x, y, z) = sin( ax x) sin( by y) sin( cz z)
2m a 2 b 2 c 2 abc

3) Show that; 〈 r 〉 = 12 (iˆa + ˆjb + kˆc) and 〈 p〉 = 0 . Then discuss the degeneracy.
1-3 Harmonic Oscillator

According to classical mechanics, L.H.O. defined as ; a particle of

mass m executing small oscillation under the action of the restoring
force: F = −k x . Where k is the proportional constant which called force
constant or Stiffness. The physical meaning of the minus sign is that the
force F in a direction opposite with particle displacement x.
The problem of H.O. in quantum mechanics has a very importance
due to many systems can be represented approximately as a harmonic
oscillators such as atomic vibrations in molecules and solid bodies,
vibrations of the electromagnetic radiation, …, etc.

1-3-1Classical Theory of L.H.O.

From Newton’s second law, equation of motion of H.O. can be setup to

be:
&x& + ω 2 x = 0 , ω = k
m

Where ω is the angular frequency. With the solutions: x = a cosωand

t
x = a sin ωt , which represent an oscillatory motion of angular frequency ω
and amplitude a. The potential is related to the force by:
∂v
F=−
∂x
So that:
1
V(x) = − mω 2 x 2
2
Which is a parabolic curve. Hence the total energy is:
1 1 1
E = T + V(x) = mx& 2 + mω 2 x 2 E= mω 2 a 2
2 2 2

Notes:
1) The minimum energy of H.O. is zero.
2) The energy of H.O. has a continuous spectrum of values.
3) The probability density of finding the oscillating particle has an
inverse proportionality with its speed.
1-3-2 Quantum Theory of H.O.

Schrodinger equation Hˆ ψ n = E nψ n for this system take the form;

−h2 ∂ 2 1
{ 2
+ mω2 &x& 2 }ψ n = E n ψ n
2m ∂x 2

mω x 2E n
Assume that; y= h and εn = hω
...........(1 - 1)

One may reach:

∂ 2ψn
+ (ε n − y 2 )ψ n = 0 ..............(1 - 2) (Why?)
2
∂y

I) Schrödinger Treatment

For the special case when y >> єn equation (1-2) reduced to ;

∂ 2 Ψn
− y 2 Ψn = 0 ................(1 - 3)
2
∂y

However, this sort of equation admits a solution of the form;

1
− y2
Ψn (y) = e 2 ...................(1 - 4)

In order to reach the exact solution of equation (1-2), one must multiply
equation (1-4) by a dummy function such as f(y) as follows;
1
− y2
Ψn (y) = f(y) e 2 ............(1 - 5)

When equation (1-5) substituted in equation (1-2) one can find that:
2 2
f(y) = H n (y) = (-1) e y dn e-y
dy n

Where ε n = 2 n + 1 and n = 0,1,2,3,... Actually, this is a Hermit polynomial

of degree n. the energy eigen values strictly can be deduce From equation
(1-1) to be;
E n = hω(n + 12 ).........(1 - 6)

This equation represent the total energy of the harmonic oscillator. It is

seen that this energy is quantized and the minimum energy that the H.O.
can take is:
E0 = 12 hω ≡ zero point energy
However, the normalized wave function of H.O. is:
1
− y2
Ψn (y) = N n e 2 H n (y)............(1 - 7)

Where N n is the normalized constant. The figure below reveal a

simplified diagram clarifying the potential energy curve and the eigen
values, eigen wave functions curves of the first three states of the H.O.
system.
H.W
1) By using the definition of the generation function show that:
1 mωωh 1/2
Nn = ( n
)1/2 and Nn = ( n
)
2 n! π 2 n! π
2) Prove that:
dH n (y) 1
a- dy
= 2n H n-1 (y) b- yH n (y) = 2 H n +1(y) + nH n-1(y)
n n +1 Ψ dΨ n (y)
c- yΨn (y) = 2
Ψn −1 (y) + 2 n +1 (y) d- dy
= -yΨ n (y) + 2n Ψ n −1 (y)

1 (y + d )Ψ (y) = n Ψ n -1 (y) 1 d )Ψ (y) = n + 1 Ψ

(y - dy
e- 2 dy n f- 2 n n +1 (y)

The two operators in (e and f) are called respectively Destruction ( â )

and Creation ( â + ) Operators. Accordingly;

3)Show that;

a- aˆ = (2mhω ) −1/ 2 (mωx̂ + ip̂ x ) b- aˆ + = (2mhω ) −1 / 2 (mωx̂ − ip̂ x )

c- [aˆ , aˆ ] = 1
+ d- Ĥ = hω(â +â + 12 )
1/2 +
e- x̂ = (h/2mω)1/2 (â + + â) f- p̂ x = − i( h m ω / 2 ) ( â − â )

4) Given Ô n = â + â . Find the commuter operators of this operator with

each of â + and â separately and thereafter find its eigen value for any
vibrating state n.

5) Depending on the creation and destruction operators investigate the

HO system in detail. ( What this approach named? )

6) Compare between Classical and Quantum Results of H.O.

1-4 Central Potentials

This is a more realistic problem compared with the previous

applications. Such sort of systems known classically by A Central
Potential Systems while in quantum mechanics called Spherically
Symmetrical Potentials. However, it defined as that type of systems
which their potentials only depend on the radial displacement between
the particle and the system origin. Mathematically this means
that ( V (rv ) = V (r ) ).
Actually, the SE for these systems can be put as in the following
expression;
−h 2 2 v v
{ ∇ + V (r )}ψ n (r ) = E n ψ n ( r) ...........(1 − 8)
2m

It is more convenient to use the spherical polar coordinates rather than

Cartesian one to deals with such a problems. However it is well known
that;
x ⇒ r(0 → r) y ⇒ θ(0 → π) z ⇒ ϕ (0 → 2 π)
radial co. zenithal co. azmuthal co.
The converting equations between the two coordinates systems are;

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

Or inversely:

r = ( x 2 + y 2 + z 2 )1 / 2 {
θ = tan −1 ( x 2 + y 2 )1/ 2 / z } ϕ = tan −1{y / z}1/ 2

Schrödinger equation in the new coordinate system can be written as:

−h 2
2m
{1 ∂ (r 2 ∂
r ∂r ∂r
)+ 1 ∂
r 2 sin θ ∂θ
( sin θ ∂∂θ ) + 1 ∂2
r 2 sin 2 θ ∂ϕ 2
}Ψ(r,θ,ϕ) +
V(r)Ψ(r , θ , ϕ ) = EΨ(r , θ , ϕ ) ......(1 - 9)

The method of separation of variables is standard approach usually used

to solve this partial differential equation. Accordingly the wave function
must be written in the form:
Ψ (r , θ , ϕ ) = R(r ) Θ(θ ) Φ(ϕ )
= R (r ) Y(θ , ϕ ) ...........(1 - 10)

The substituting of equation (1-10) in (1-9), will splitting Schrödinger

equation to the following three differential equations:

dR ( r )
d (r 2 ) + 2 mr 2 ( E − V ( r )) R ( r ) = λ R ( r ) .............(1 - 11)
dr dr h2

1 d dΘ(θ ) µ
sin θ dθ
(sin θ )+ (λ − )Θ(θ ) = 0 ..............(1 - 12)
dθ sin 2 θ

d 2 Φ (ϕ )
+ µΦ (ϕ ) = 0 ..............(1 - 13)
dϕ 2

Where λ and µ are constants. Solutions of zenith and azimuth part

respectively given by;

Θ(θ ) = Plm (ω ) = { 2l +1 (l-|m|)! }1 / 2 (1 − ω ) |m|/ 2 ddω

| m|
Pl (ω ) .......(1 - 14)
2 (l +|m|)! | m|

Φ (ϕ ) = ( 2π ) −1 / 2 e imϕ ..........(1 - 15)

Where
µ = m2

λ = l (l + 1)
m = 0,±1,±2,±3,... ⇒ Magnetic Quantum Number
 l = 0,1,2,3,..., ≥| m | ⇒ Orbital Quantum Number
ω = cos θ
1 dl
Pl (ω ) = {(ω 2 − 1)} ⇒ Legendre Polynomial
l dω
2 l!
d |m|
Plm (ω ) = (1 − ω 2 ) |m|/ 2 Pl (ω ) ⇒ Associated Legendre polynomial
dω |m|

H.W:
1)Set up the first six associated Legendre polynomial.
2)Show that;
1 0 l′ ≠ l
∫ Plm (ω ).Plm
′ (ω ).dω = 2 ( l +|m|)!
2l +1 ( l −|m|)!
l′ = l
−1

1-4-1 Spherical Harmonics

Spherical Harmonics function is simply the product result of zenithal

times azimuthal parts of the wave function. i.e.

Ylm (θ , ϕ ) = Plm (ω ) ⋅ Φ m (ϕ )
= N lm Plm (ω ) e imϕ

The factor N lm appears in last equation is the normalization constant and

it so easy to prove that it given by;

N lm = ( − 1) ( m + |m |) / 2 {
2 l +1 (l- |m |)!
4 π (l + |m |)!
}1/ 2
(Prove)

H.W:
1) What is the physical meaning of the arbitrary factor appears in the last
equation?
2)Set up the first six spherical harmonics functions.
3)Show that the degeneracy of spherical harmonics is (2l+1) and the
parity is (-1)l.
1-4-2 Angular Momentum

A according to classical mechanics any particle moves with

v
momentum paround a fixed origin has an angular momentum;
v v v
L = r ×p
v
This classical angular momentum L goes over into a quantum
mechanical L̂ in the usual way:
Lˆ = r̂ × p̂

Thus, it easy to prove that:

lˆx = ypˆ z - zp̂ y = -ih(y ∂∂z - z ∂∂y )

lˆy = zpˆ x - xp̂ z = -ih (z ∂∂x - x ∂∂z )

lˆz = xpˆ y - zp̂ x = -ih (x ∂∂y - y ∂∂x )

Considering spherical polar coordinate one can easy, but tedious, to

rewrite the above equations in the form;
lˆx = ih (sinϕ ∂∂θ + cotθ cosϕ ∂ )
∂ϕ

lˆy = ih (-cosϕ ∂∂θ + cotθ sin ϕ ∂ )

∂ϕ
lˆz = -ih ∂
∂ϕ

Typically, it is convenient to write; Lˆ2 = lˆx2 + lˆy2 + lˆz2so,

Lˆ2 = −h 2 { 1 ∂
sin θ ∂θ
(sin θ ∂ )+ 1
∂θ
∂2
sin θ ∂ϕ 2
2 } (Prove)

In fact, Spherical Harmonics are an eigen wave function for

operator L̂2 with an eigen values h 2 l (l + 1) where,

Lˆ2Ylm (θ , ϕ ) = h 2 l (l + 1).Ylm (θ , ϕ ) ..............(1 - 16)

HW:
Depending on procedure by means equations (1-12 and 13) produced,
derive equation (1-16).
Furthermore, spherical harmonics is also eigen wave function for the z-
component of angular momentum. i.e.

lˆz Ylm (θ , ϕ ) = mh.Ylm (θ , ϕ ) ..............(1 - 17) (Prove)

Now concerning with equations (1-16 and 17) and recall the conditioned
value l = 0,1,2,3,..., ≥| m | it is seen that for each value of l defining a sub
state for L there are m distinct arrangements of lz arranging from - l to l
through the zero value. ( Do you hear by Space Quantization? Or the
Zeeman Effect?)

It should be mentioned that the procedure by means equations (1-12 and

13) are solved is a typical same for any system have a spherical potential
irrespective of the mathematical nature of this potential. While equation
(1-11) can't be solved without a precise knowledge of the mathematical
form of this potential. So, concerning with this point, two different
applications will be discussed in the following two sections.

1-4-3 Particle in A potential Sphere

This is a more realistic problem compared with the HO problem.

However, the potential for such a case beings as in following formula;

zero r<a
V(r) = [
∞ r ≥ a Where one may met such a system?

It is obvious that the particle can not be penetrated the spherical potential
barrier and it is bounded to move only inside the sphere (Can you show
how the wave function beings zero out side the sphere?). Therefore,
equation (1-11) becomes;
dR ( r )
d
dr
(r 2 dr
) + 2 mr 2
h2
( E − zero) R(r ) = λR(r ) .............(1 - 18)

and hence,

d (r 2 dR ( r ) 2mEn
dr dr
) +{ 2
r 2 − l (l + 1)}R( r ) = 0 ...............(1 - 19)
h
 2mEn
Assuming k2 = to get;
h2
dR ( r )
d
dr
(r 2 dr
) + {k 2 r 2 − l ( l + 1)} R ( r ) = 0 .......... ....(1 - 20)

Or; d 2 R (r ) dR (r )
2
r 2
+ 2r + (k 2 r 2 − l (l + 1)) R (r ) = 0 ..............(1 - 21)
dr dr
= ( dr ) 2
dρ d2 dρ d2
Assuming ρ = kr so drd = dr ddρ and dr 2 dρ 2 hence equation
(1-21) when ν = l (l + 1) becomes;
2 d 2 R( ρ ) dR( ρ )
ρ 2
+ 2ρ + ( ρ 2 − ν ) R( ρ ) = 0 ..............(1 - 22)
dρ dρ
In fact equation (1-22) is the Modified Bessel Equation of Order ν where
its general solution given by;
R ( ρ ) = c1Jν ( ρ ) + c2 Iν ( ρ ) ..............(1 - 23)
Obviously, Jν(ρ) are Spherical Bessel's Functions of the First Kind
while Iν(ρ) are Spherical Bessel's Functions of the second Kind.
It is seen that second term in last equation must be drop so as to obtain a
reliable solution ( Why?). So,
R ( ρ ) = N1Jν ( ρ ) ..............(1 - 24)

H.W:

1) With the aid of last equation and the physics of problem show that the
energy eigen values can be expressed by;
h 2α 2
E= ..............(1 - 25)
2ma 2
Where α≡ρ is the value that make Bessel's Function vanishes at r=a.

2) Find the normalization constant N1 and then deduce the final form of
the eigen wave functions for such a system by combining equation (1-24)
together with equations (1-14 and 15).
1-4-4 Hydrogen Like Atoms

It is well known that these atoms have only one electron moves around
their nucleus under the action of Coulomb’s force: F = k/r 2 . Thus, the
potential of these atoms has the form V(r) = − k/r, where k = Ze 2 /4πε 0 . It
can be seen that V(r) is only depend on the radial distance between the
electron and the nucleus. So, it is an another example for the spherically
symmetrical potential systems. Equation (1-11) for this type of central
potential systems becomes;
dR ( r ) l ( l +1)
1 d (r 2 ) + { 2 m2 ( E + kr ) − }R ( r ) =0 .......... ...(1 - 26)
r 2 dr dr h r2

This equation can be easily solve, but tedious, and the solution may put in
the form;
(n -l-1)!
R(r ) ≡ R( ρ ) = −{ α 2
2n{(n + l)!}3
}1 / 2 e − ρ / 2 ρ l L2nl++l1 ( ρ ) ............(1 - 27)

2Z r
Where L2nl++l1 ( ρ ) is Associated Lagurre Polynomial and ρ = α r = na with 2
4 πε h 0

Z beings the Atomic Number and a 0 = me Boher Magneton. For 0

2

q=n+1 and p=2l+1 associated Lagurre function may expressed by the

form;
dp
Lqp ( ρ ) = Lq ( ρ )
dρ p

Where Lq ( ρ ) is Lagurre Function which expressed in the form;

dq
Lq ( ρ ) = e ρ (ρ q e −ρ )
q
dρ
H.W:

1) Set up the first five associated Lagurre functions.

2) With aid of equations (1-14, 15 and 27) deduce the final form of the
eigen wave functions for H-like atoms.
3) Show that the eigen values for such a system are given by the
formula; h 2z 2
En = −
2ma 20 n 2
4) Concerning with radial part wave function state the reason behind the
condition; n = ν + l + 1
1-5 Rigid Rotator

Simply, this system compromise on a freely particle ( or more )

which rotate a round fixed point. (When you may met such a system?).
So, SE for this system is;

Hˆ Ψn (r , θ , ϕ ) = E n Ψn (r , θ , ϕ )

h 2∇ 2 z
− Ψn ( r , θ , ϕ ) = E n Ψn ( r , θ , ϕ )
2m

−h 2
2m
{ ∂∂ (r
1
r r
2 ∂
∂r
)+ 1 ∂
r 2 sin θ ∂θ
( sin θ ∂∂θ )

1 ∂2
r 2 sin 2 θ ∂ ϕ 2
}Ψ(r,θ, ϕ) = EΨ (r , θ , ϕ ) θ
rr p
2 r
−h ∂ 2 }. y
{ 21 ∂ ( sin θ ∂ )+ 1
2m r sin θ ∂θ ∂θ r sin θ ∂ϕ 2
2 2

Ψ(r,θ,ϕ) = EΨ (r , θ , ϕ )
x φ
2
−h 2
{ sin1 θ ∂ ( sin θ ∂∂θ ) + 1 ∂ }Ψ(r,θ,ϕ)
2 ∂θ sin 2 θ ∂ϕ 2
2mr
= EΨ ( r , θ , ϕ )

−h 2 ∂ 2 }Ψ(θ,ϕ) =
{ sin1 θ ∂ ( sin θ ∂∂θ ) + 1 EΨ (θ , ϕ )
2 ∂θ sin 2 θ ∂ϕ 2
2mr

−h 2 1 ∂ 1 ∂ 2 }Ψ(θ,ϕ) =
{ ( sin θ ∂∂θ ) + EΨ (θ , ϕ )...........(1 − 28)
2 I sin θ ∂θ sin 2 θ ∂ϕ 2

Where I=mr2 is the moment of inertia. It can be seen that the Hamiltonian
of the system under consideration is;
ˆ Lˆ2
H =−
2I
Obviously the term in numerator is the angular momentum operator
which previously proved to be;

Lˆ2 = −h 2 { 1 ∂
sin θ ∂θ
(sin θ ∂ )+ 1
∂θ
∂2
sin θ ∂ϕ 2
2 }
Equation (1-28) need further simplification in order to be solvable ( What
that simplification called?). Consequently, to achieve this task multiply
this equation by (-2I sin2θ/ћ2 ), so it reduces to the following form;
{sin θ ∂
∂θ
( sin θ ∂
∂θ
)+ ∂ 2 }Ψ(θ,
∂ϕ 2
ϕ ) + κ sin 2 θ Ψ (θ , ϕ ) = 0 ......( 1 − 29 )

Certainly (κ=2.I.E/ ћ2). Using the separation of variables to solve this

equation through assuming;

Ψ (θ , ϕ ) = Θ(θ ) Φ (ϕ ) ..............(1 - 30)

New the substitution of equation (1-30) into (1-29) will yield to;
sin θ 1
∂
∂θ
( sin θ ∂Θ
∂θ
) + κ sin 2 θ = − ∂ 2Φ
∂ϕ 2
......( 1 − 31 )
Θ Φ

Mathematically this means that; ( Why?)

sin θ ∂
∂θ
( sin θ ∂Θ
∂θ
) + κ sin 2 θ = m 2 ......( 1 − 32 )
Θ
1
− ∂ 2Φ
∂ϕ 2
= m2 ......( 1 − 33 )
Φ

The general solution of equation (1-33) take the form;

Φ (ϕ ) = A e im ϕ
The singularity condition requested that;
Φ (ϕ ) = Φ (ϕ + 2π )
Therefore;
A e im ϕ = A e im (ϕ + 2π )
With the aid of Euler's theorem one may conclude that;
m = 0 , ± 1, ± 2, ± 3,...
In order to find the value of A, the normalization condition must be used.
i.e.
2π

∫ Φ m ⋅ Φ m dτ = 1
∗

However, one can directly find that; A =1 2π

So, the final form of the azimuthally function being as follows;

Ψm (ϕ) = 1 eimϕ .........(1 - 34)

2π
Concerning with the equation (1-32), assume that ω=cosθ and replace
θ(θ) by P(ω), as did before, the equation can be rewritten as in form
below;

(1 − ω 2 ) ddωP2 − 2ω
2 2
dP
dω
+ {κ − 1 −mω 2 } P = 0 ......( 1 − 35 )

It is well known that, equation (1-35) is Associated Legendre's

Differential Equation when κ = l (l + 1) . Anyway, it reduces to what
be known by Legendre's Differential Equation for m=0. However, its
solution given by equation (1-14). Hence the total wave function beings
as in the form;

Ψlm (θ , ϕ ) ≡ Ylm (θ , ϕ ) = Plm (ω ) ⋅ Φ m (ϕ )

= N lm Plm (ω ) e imϕ
Where;
N lm = ( − 1) ( m + |m |) / 2 { }
2 l +1 (l- |m |)!
4 π (l + |m |)!
1/ 2

H.W:
1) Express Pl mas a power series in ω ( i.e. Pl = ∑ l = 0 a l ω ) and hence
m l

verify the convergence of the series. Then prove that κ = l (l + 1) for

ℓ beings 0, 1, 2, 3, …
2) Repeat the approach in (1) to prove that the solution of equation
(1-32) is given by equation (1-14).
3) What is the unit of κ?!.

The energy eigen values for the rigid rotator can be found from the
equation that defined κ variable as follow;
2 IE
κ = = l ( l + 1)
So, h2
h 2 l (l + 1) h 2 l (l + 1)
E= or El =
2I 2I
H.W:
1) Discuss why energy eigen values equation do not shows any
dependant on m.
2) Can you deduce the last equation directly from equation (1-28).
Why?
1-6 Selection Rules

Transition in certain dynamical variable from a specific state to

another different one is not always possible. So, it is important to know
the procedure by which these transitions are allowed or not. For example
one may start with a molecule modulated to be a harmonic oscillator
since it is a simple one. However, this may corresponds to absorption or
transmission of infrared radiation. The question now is what the
restrictions in the transition of the dipole moment for the case under
consideration. Initially, lets neglect the rotational and consider vibrational
transitions and start with expanding µ by McLaren's series around the
equilibrium nucleus separation as follows;

µ ( x) = µ ( x 0 ) + µ ′( x 0 ) ⋅ x + ⋅ ⋅ ⋅ What the physical meaning that could be

realized from this expansion?

Then the dipole moment transition considering the first two terms is;
µ nm = 〈n | µˆ | m〉

µ nm = 〈 n | µ 0 | m 〉 + µ 0′ 〈 n | xˆ | m 〉

µ nm = µ 0 δ nm + C 〈 n | (â + + â ) | m 〉

µ nm = C 〈 n | ( â + + â ) | m 〉 where C = µ 0(h/ 2mω)1/ 2

µ nm = C {〈 n | â + | m 〉 + 〈 n | â | m 〉

µ nm = C { m + 1 ( m + 1) 〈 n | m + 1〉 + n 〈 n | m − 1〉}

µ nm = C { m + 1 ( m + 1)δ n , m + 1 + n δ n , m − 1 }

So the only non-zero matrix element are those for which m=n±1. Hence the
selection rules for these transitions are;
∆n = ± 1

Concerning with the rotational transitions a similar approach can be

followed if a diatomic molecule is modulated as a rigid rotator. Typically,
this situation will govern the transitions and absorption in the range of far
infrared or microwave radiation. For simplicity one may assume that the
field is polarized in one dimension , say z, for example. Then dipole
moment will take the form;
µ = µ 0 cos θ Which direction is that?

So,
µ l′m′, lm = 〈l ′m′ | µˆ | lm〉

µ l′m′, lm = µ 0 〈l ′m′ | cosθ | lm〉

Making use the identity;

m m
cos θ | l , m〉 = al | l − 1, m〉 + bl | l + 1, m〉
One can directly obtain;
m m
µl ′m ′, lm = µ 0 a l 〈l ′m′ | l − 1, m〉 + µ 0 b l 〈l ′, m′ | l + 1, m〉

m m
µl ′m ′, lm = µ 0 a l δ m ′mδ l ′,l −1 + µ 0 b l δ m ′mδ l ′, l +1

It can be seen that the non-zero matrix element of µ are those for which;

∆m = 0 and ∆l = ± 1

Which are the selection rules for rigid rotator.

H.W:
Deduce the dipole moment selection rules for a molecule considering
its rotation and vibration motion together. Hint; Use the assumption
µ ( x) = (a + b ⋅ q) cos θ where a and b are constants.
1-7 Matrix Representation

Formulation of Q.M. in terms of matrices is an important

mathematical tool usually used to simplifies the analyses. This procedure
,however, starts with writing operators and wave function as a matrices.
To do so it is often useful to recall that any vector such as A in N-
dimensions can be represent as:
n
A = η1 A1 + η 2 A2 + η 3 A3 + ...... + η n An = ∑ η i Ai
i =1
Where η1 ,η 2 ,....,η n are unit vectors satisfying the relation; η n .η m = δ nm .
It is seen that η1 ,η 2 ,....,η n form a BASIS in defining the vector in both
magnitude and direction. Accordingly the scalar product of two vectors
A and B can be represented by a matrix notation as shown bellow;

 B1 
 
 B2 
  
A.B = A1 B1 + A2 B 2 + ..... + An B n =  A1 A2 A3 .... An  B3
  
 . 
B 
 n
Matrix of A Matrix of B

Also the basis can be put in matrix form as follows;

1 0  0 
     
0   1 0 
η1 =  0  , η 2 =  0  ,……., η n =  0 
     
 .  .  .
0  0   1
     

Such that;
1
 
 0
  
η1 ⋅ η1 = 1 0 0...0  0 = 1 ⇒ normalized
  . 
 0
 
and
 0
 
1
  
η1 ⋅ η 2 = 1 0 0...0  0 = 0 ⇒ orthogonal
  . 
 0
 

Regarding the formulation of operators and wave functions in terms

of matrices, the complete orthonormal eigen wave functions ϕ i have to
be considered as a BASIS in a way similar to that for the unit vectors. So,

〈ϕ i | ϕ j 〉 = δ ij
n
ψ = c1ϕ1 + c2ϕ2 + c3ϕ3 + .....+ cnϕn = ∑ciϕi
i=1

n
U = b1ϕ1 + b2ϕ 2 + b3ϕ3 + ...... + bnϕ n = ∑ biϕ i
i =1

The overlap integral of ψ and U is;

n m
〈ψ | U 〉 = ∑ ∑ ci*b j 〈ϕi | ϕ j 〉
i =1 j =1

= ∑∑ c*i b jδ ij
i j

〈ψ | U 〉 = ∑ ci*bi
i

= c1*b1 + c*2 b2 + ....... + c*nbn

 b1 
 
 b2 
(
〈ψ | U 〉 = c1* c *2 .... c *n  
.
)
 
 bn 
Matrix of ψ Matrix of U

The basis in matrix form are;

  1 0  0 
     
0   1 0 
ϕ1 = 0 , ϕ 2 = 0 , ……, ϕ n =  0 
   
     
 .  .  .
0  0   1
     

∧
The operator A defined by;
∧
Aψ = U
∧
A ∑ ciϕi = ∑ biϕi
i i
∧

∑ c ϕ Aϕ = ∑ b ϕ ϕ
i
i
*
j i
i
i
*
j i

∧
∑ ci 〈ϕ j | A | ϕi 〉 = ∑ bi 〈ϕ *j | ϕi 〉
i i
= ∑ biδ ji
i

∑ c ( A)
i
i ji = bj
Where j = 1,2,3,.....,n

Note: One have to recall that most of operators in Q.M. are Hermitean
because it represents a real physical quantity. i.e. A ji = Aij*
∧
Proof: A ji = 〈ϕ j | A | ϕ i 〉
∧
= ∫ ϕ *j Aϕi dτ
∧
= ∫ ϕi ( Aϕ j )* dτ
*

= ∫ ϕi* Aϕ j dτ 
∧

 
*
 ∧  *
= 〈ϕ i | A | ϕ j 〉  = Aij
 

For j=1 c1 A11 + c2 A12 + .... + cn A1n = b1

j=2 c1 A21 + c2 A22 + .... + cn A2 n = b2
j=3 c1 A31 + c2 A32 + .... + cn A3 n = b3
 ……………………………
……………………………
c1 An1 + c2 An 2 + .... + cn Ann = bn
In matrix form;
 A11 A12 .... A1n   c1   b1 
    
 A21 A22 .... A2 n   c2   b2 
 .... ..... .... ....   .  =  . 
     
 An 1 An 2 .... Ann   cn   bn 
∧
Matrix of A Matrix Matrix
of ψ of ϕ

Where each element A ji is called matrix element.

The set of quantities A ji with all possible j and i values is called

matrix of  (or matrix of the quantity A), and each of A ji is called the
matrix element which corresponds to the transition from state j to state i.
∧
Now if the basis ϕ i are an eigen function of A . i.e.

∧
A ϕi = aiϕ i
∧
( A )ji = 〈ϕ j \ A ϕi 〉 = ai 〈ϕ j \ ϕi 〉 = aiδ ji
A ji = [ a j ,i = j
0 ,i ≠ j

∧
Then the matrix of A is diagonal

 A11 0 0 .... 0 
 
∧
 0 A22 0 .... 0 
A=
.... .... .... .... .... 
 
 0 0 0 .... Ann 
1-7-1 Angular Momentum
Recall that;
∧2
L Ylm = h 2 l( l + 1 )Ylm
∧2
( L )m′ ,m = h 2l( l + 1 )δ m′ ,m
= alδ m′ ,m
∧ 2 ∧ 2
Then the only non- zero matrix elements of ( L ) are ( L )m′ ,m which
equal to h 2l( l + 1 ) where l = 0 ,1,2 ,....,n − 1 and m = 0 ,m1,m2 ,.....,ml

 al 0 0 .... 0
 
∧2
 0 al 0 .... 0
L =  0 0 al .... 0
 
 .... .... .... .... ....
0 0 0 .... al 

∧
For the z- component l z
∧
l z Ylm = mhYlm
∧
( l z )m′ ,m = mhδ m′ ,m
∧ ∧
Then the non- zero matrix element of ( l z ) are ( l )m′ ,m which equal to mh ,
where m = 0 ,m1,m2 ,.....,ml

0 0 0 .... 0 
 
∧
 0 mh 0 .... 0 
lz =  0 0 m 2h .... 0 
 
 .... .... .... .... .... 
0 .... m lh 
 0 0

∧
Since the spherical harmonics Ylm is not eigen functions of l x and
∧ ∧2
l y , then there matrices can not be found directly as in the case for L and
∧
l z . However, to do so one have to define the following operators;
∧ ∧ ∧ ∧ ∧ ∧
l + = l x + i l y and l − = l x − i l y
Now;
 l∧ z ,l∧ +  = l∧ z l∧ + − l∧ + l∧ z
 
∧ ∧ ∧ ∧ ∧ ∧
= lz ( lx + i l y ) − ( lx + i l y )lz
∧ ∧ ∧ ∧ ∧ ∧ ∧ ∧
= l z l x − l x l z + i( l z l y − l y l x )
∧ ∧
= ih l y + i( −ih l x )
∧ ∧
= h( l x + i l y )
∧
= h l+ ..............(1 − 36)

H.W: Prove that; l z ,l −  = −h l − ..........(1 − 37)

∧ ∧ ∧

 
From equation (1-36)
∧ ∧ ∧ ∧ ∧
l z l+ = h l + + l+ l z
∧ ∧ ∧ ∧ ∧
l z l + Ylm = h l + Ylm + l + l z Ylm
∧ ∧
= h( l + Ylm ) + mh( l + Ylm )
∧
= h( m + 1 )( l + Ylm )
∧
It is seen that the function ( l + Ylm ) is an eigen function of the operator
∧
( l z ) with an eigen value ( m + 1 )h . Similarly one can find that;
∧ ∧ ∧
l z ( l − Ylm ) = ( m − 1 )h( l − Ylm )
∧ ∧
Where the function ( l − Ylm ) is an eigen function of the operator ( l z ) with
an eigen value ( m − 1 )h. Now let,

∧ ∧ ∧
So, l z ( l + Ylm ) = α l z Ylm′
= αm′hYlm′
But,
∧ ∧ ∧
l z ( l + Ylm ) = ( m + 1 )h( l + Ylm )
= ( m + 1 )hαYlm′
Then
( m + 1 )hαYlm′ = αm′hYlm′ ⇒ m′ = m + 1
Hence;
∧
l + Ylm = αYlm+1
∧
This means that ( l + ) is a creative operator since it turns Ylm to Ylm+1 .
∧
therefore the non-zero matrix elements of l + are;
 ∧
( l + )m+1,m = α .............(1 − 38)
In a similar procedure if it is assumed that;
∧
l − Ylm = αYlm′
∧ ∧ ∧
So, l z ( l − Ylm ) = α l z Ylm′
= αm′hYlm′
But,
∧ ∧ ∧
l z ( l − Ylm ) = ( m − 1 )h( l − Ylm )
= α ( m − 1 )hYlm′
Then
αm′hYlm′ = α ( m − 1 )hYlm′ ⇒ m′ = m − 1
This means:
∧
l − Ylm = αYlm−1
∧
So, one can say that the operator ( l − ) is a destructive operator when it is
operator on Ylm will turn it to Ylm−1 and the non-zero matrix element of
∧
( l − ) are;
∧
( l − )m−1,m = α ............(1 − 39)
From equation (1-38) and (1-39) we find;
∧ ∧
( l + )m+1 ,m = ( l − )m−1,m = α .............(1 − 40a)
Or equivalently;
∧ ∧
( l + )m ,m−1 = ( l − )m ,m+1 = α .............(1 − 40b)

In order to find α we have to trace the following procedure;

∧ ∧ ∧ ∧ ∧ ∧
l + l − = ( l x + i l y )( l x − i l y )
∧2 ∧2 ∧ ∧ ∧ ∧
= lx + l y − i l x l y + i l y l x
∧2 ∧2 ∧ ∧ ∧ ∧
= l x + l y + i( l y l x − l x l y )
∧2 ∧ ∧
2
=L −l z+ hlz
Now;
∧ ∧ ∧2 ∧ ∧
l + l − \ lm〉 = L \ lm〉 − l 2 z \ lm〉 + h l z \ lm〉
{
= h 2 l(l + 1) − h 2 m 2 + h 2 m | lm〉 }
∧ ∧
〈 l ′m′ | l + l − {
| lm〉 = h 2 l(l + 1) − m 2 + m δ l ′lδ m ′m }
∧ ∧
( l + l − )mm = h 2 ( l + m )( l − m + 1 ) .............(1 − 41)
From the definition of matrix multiplication we have;
∧ ∧ ∧ ∧
( l + l − )mm = ∑ ( l + )mn ( l − )nm
n

From equation (1-41) one find;

2

( l + l − )mm = ( l + )m ,m+1 .( l − )m−1,m = ( l + )m ,m−1 

∧ ∧ ∧ ∧ ∧
..........(1 − 42)
 
From equations (1-41) and (1-42) one have;
∧ 1
α = ( l + )m ,m−1 = h{( l + m )( l − m + 1 )} 2 ........(1 − 43a)
Or;
∧ 1
α = ( l − )m−1,m = h{( l + m )( l − m + 1 )} 2 ........(1 − 43b)
∧ ∧
Now we can find the matrix elements of ( l x ) and ( l y ) as follows;
∧ ∧ ∧
l++ l− = 2lx
∧ ∧ ∧
2 l x Ylm−1 = l + Ylm−1 + ( l − )m ,m−1
∧ ∧
It had been found that the non-zero matrix elements of ( l + ) and ( l − ) are
∧ ∧ ∧
those; ( l + )m ,m−1 and ( l − )m+1,m . Thus the non-zero matrix elements of l x
are;
∧
1 ∧ h 1
( l x )m ,m−1 = ( l + )m ,m−1 = {( l + m )( l − m + 1 )} 2
2 2
Or;
∧
1 ∧ h 1
( l x )m−1,m = ( l − )m−1 ,m = {( l + m )( l − m + 1 )} 2 (Prove)
2 2
∧ ∧ ∧
l + − l − = 2i l y
∧ ∧ ∧
2i( l y )m ,m−1 = ( l + )m ,m−1 − ( l − )m ,m−1
∧
1 ∧
∴ ( l y )m ,m−1 = ( l + )m ,m−1 = α
2i
− ih 1
= {( l + m )( l − m + 1 )} 2
2
Or;
∧ ∧ ∧ ∧
2i( l y )m−1,m = ( l + )m−1 ,m − ( l − )m−1 ,m = −( l − )m−1,m = α
∧
ih 1
( l y )m−1 ,m = {( l + m )( l − m + 1 )} 2
2
∧ ∧
∴ ( l y )m ,m−1 = −( l y )m−1,m
1-7-2 Spin Angular Momentum

Indeed analytical investigation of spin angular momentum is an

advanced problem in Q.M. and required to start from Dirac's equation
rather than S.E.. But, by making use a simple comparison between orbital
and its counterpart spin angular momentum one may reach a considerable
results. In accordance to equations (1-16 and 17) and the physical
concept of the angular momentum one can set up the following equations;

∧2
S α ms = h 2 s( s + 1)α ms
and,
S z α ms = mms hα ms
Where,
s = 12 and m s = ± 12
However, α1/2 and α-1/2 are spin wave functions for spin up and down
respectively. So,
∧2 Ŝ zα 1 = 12 hα 1
3 2
S α±1 = h α±1 4
and 2 2

2 2
Ŝ zα − 1 = − 12 hα − 1
2 2

For simplicity one may assume α1/2 =α1 and α-1/2 =α2 . Hence,

i = 12
α= ∑ ci α i
i =− 12
α = c α + c− α −
1
2
1i 1
2
1i
2 2

α = c1α 1 + c 2α 2

2
I) Matrix of Ŝ

∧2 ∧2
2
According to, S α1 = h s( s + 1)α 1 and S α 2 = h 2 s (s + 1)α 2
One may built up the matrix of this operator to be;

∧2  ( Sˆ 2 ) 3 2
( Sˆ 2 )12   4 h 0  3 2  1 0
S =  2 11 = = 4h  
ˆ ( Sˆ 2 ) 22   0 3 h2
0 1 
( S ) 21 4 
II) Matrix of Ŝ z

Similarly, with aid of equations,

∧ ∧
S z α 1 = 12 hα 1 and S z α 2 = − 12 hα 2

Matrix of this operator can be built as in the form;

∧  (Sˆ ) (Sˆ z )12   12 h 0  1 1 0  1

S z =  z 11  =  = h  = hσˆ z
ˆ ( Sˆ z ) 22   0 − 12 h  2 0 − 1 2
(S z ) 21

Now,

∧ α  1 0  α1  1 α1  1  α 1 
S z  1  = 12 h     = 2 h α  = 2 h − α 
α 2  0 − 1 α 2   2  2

III) Matrix of Ŝ x

Assume that;
∧ ∧
S x α 1 → α1′ and S x α 2 → α 2′

Which can be given as a linear superposition in terms of spin up and spin

down wave functions as follows;

∧
α1′ = S x α 1 = a11α 1 + a12α 2 .............(1 - 44)
∧
α 2′ = S x α 2 = a11α1 + a12α 2 .............(1 - 45)

From equation (1-44);

∧
( S x )11 = a11δ 11 + a12δ 12 = a11
∧
( S x ) 21 = a11δ 21 + a12δ 22 = a12

While equation (1-45) gives;

∧
( S x )12 = a 21δ 11 + a 22δ 12 = a 21
∧
( S x ) 22 = a 21δ 21 + a 22δ 22 = a 22
Regarding angular momentum investigation. i.e.
∧ ∧ h 1
( l x ) m −1,m = (l x ) m,m −1 = {(l + m)(l − m + 1)} 2
2
The following formula may set up;
∧ ∧ h 1
( S x ) ms −1,ms = (S x ) ms ,ms −1 = {( s + ms )(s − ms + 1)} 2 = h
2 2
Therefore, the only non-zero matrix element of the x-component of spin
angular momentum are those for ms=1/2. i.e.
∧ ∧
( S x ) 1 ,− 1 and ( S x ) 1 , − 1
2 2 2 2

Which equal to ½ћ. Then,

∧  (Sˆ ) ( Sˆ x )12   0 1h 1 0 1 1

S x =  x 11 2
ˆ )   1 h = h
= = hσ̂ x
( Sˆ )
 x 21 ( S x 22   2 0  2 1 0 2

Now;
∧ α  0 1 α1  1 α 2 
S x  1  = 12 h     = 2 h α 
α 2  1 0 α 2   1

IV) Matrix of Ŝ y

Following a similar procedure one may get the y-component matrix

of spin angular momentum. Again assume that;
∧ ∧
S y α 1 → α 1′ and S y α 2 → α 2′

Which can be given as a linear superposition in terms of α1 and α2 as

follows;

∧
α1′ = S y α1 = a11α 1 + a12α 2
∧
α1′ = S y α 2 = a11α1 + a12α 2

Hence;
∧
( S y )11 = a11δ 11 + a12δ 12 = a11
∧
( S y ) 21 = a11δ 21 + a12δ 22 = a12
∧
( S y )12 = a 21δ 11 + a 22δ 12 = a 21
 ∧
( S y ) 22 = a 21δ 21 + a 22δ 22 = a 22

In accordance to relation;
∧ ∧ i 1
( l y ) m,m−1 = − ( l x ) m−1,m = − h{(l + m )(l − m + 1)} 2
2
The following formula may set up;
∧ ∧ i 1 i
( S x ) ms ,m −1s = −(S x ) ms −1,ms = − h{( s + m s )(s − m s + 1)} 2 = − h
2 2
Therefore, the only non-zero matrix element of the y-component of spin
angular momentum are those for ms=1/2. i.e.
∧ ∧ i
( S y ) 1 ,− 1 = - ( S y ) 1 ,− 1 = − h
2 2 2 2
2
Then,

∧  ( Sˆ ) ( Sˆ y )12   0 −ih  1 0 − i  1
S y =  y 11  = i 2
= h = hσ̂ y
ˆ ˆ
(S y ) 21 ( S y ) 22   2 h 0  2  i 0  2

Now;
∧ α  0 − i  α 1  i − α 2 
S y  1  = 12 h     = 2 h α 
α 2   i 0  α 2   1 

The matrices σx, σy, σz called Pauli's Spin Matrices.