PHY 352 QUANTUM MECHANICS II 3 Credits

Linear Harmonic Oscillator. Step Potential Barrier. Rectangular Potential Barrier. Tunnelling. Square well
Potential. Angular Momentum, Commutation relations. The Operator L and L. Kinetic Energy and Angular
Momentum. Reduction of the Central Force Problem: Eigenvalue Problems for L and L 2 Eignevalues and
Eigenfuctions of L Associated Legendre Polynomials. Simultaneous Eigenfuctions of L and L 2. Spherical
Harmonics. Vector Addition of Angular Momenta. Solution of the Radial Wave Equation Bound-State
Energy Spectrum. Degeneracy. Bound-State Eigenfunctions. Connection with Angular Momentum. Atom
in a magnetic Field. Larmor Precession. Concept of spin. Stern-Gerlah Experiment. Electron Spin.
Zeeman Effect. Spin-Orbit Interaction. Effect on the Hydrogen Energy Levels. Identical Particles in
Quantum Mechanics. Symmetric and Antisymmetric Wavefunctions: Bosons and Fermions. Bose-Einstein
and Fermi-Dirac statistics. The Pauli Exclusion. Time-Independent Perturbations. First-and Second order.
Application: The Stark Effect for a Rigid Rotator.

1. Quantum Physics of Atoms, Molecules, Solids, Nuclei and Particles. 2nd Edition
Robert Eisberg and Robert Resnick, John Wiley & Sons, New York 1985.

2. Introductory Quantum Mechanics. 9th Ed. Richard L. Liboff, Addison-Wesley Publishing

Company, California, 1989.
3. Quantum Mechanics. 2nd Ed. Amit Goswani Wm C. Brown Publishers, London, 1997.
4. Physics for Scientist and Engineers with Modern Physics. 4th Ed. Douglas C. Giancoli, Pearson
Education International, 2009.

1
 THE TIME- INDEPENDENT SHCRODINGER EQUATION (TISE)

𝑖ћ𝜕𝜓(𝑟⃗,𝑡) −ћ2
=[ 𝑣̅ 2 + 𝑣(𝑟⃗)] 𝜓(𝑟⃗, 𝑡)………………………………………1
𝜕𝑡 2𝑚

𝑖
𝜓(𝑟⃗, 𝑡) = 𝜓(𝑟⃗)𝑒 −ћ𝐸𝑡 …………………………………………………………2
Potential does not depend explicitly on the time.

Equation (2) is a solution to (1) so substitute (2) into equation (1) in other to verify.
𝑖𝐸 𝑖
− 𝑡 −ћ2 2 − 𝐸𝑡
𝐸 𝜓(𝑟⃗)𝑒 ћ =[ 𝑣̅ + 𝑣(𝑟⃗)] 𝜓(𝑟⃗)𝑒 ћ
2𝑚

Eq. (2) is a solution to (1) if 𝜓(𝑟⃗) is a solution to the 𝐷𝐸 .

−ћ2
( 2𝑚 𝑣̅ 2 + 𝑣(𝑟⃗)) 𝜓(𝑟⃗) = 𝐸𝜓………………………………………….3

Eqn. (3) is the time-independent Schrödinger equation and 𝜓(𝑟⃗) is called the study-state solution to the
Schrödinger equation. The function 𝜓(𝑟⃗)is will normally satisfy (3) for particular values of E. These values of E
−ћ2
are called the Eigenvalues of Ĥ = 𝑣̅ 2 + 𝑣(𝑟⃗) OR the energy eigenvalues.
2𝑚

To each eigenvalue will correspond one or more functions satisfying equation (3) such functions are called Eigen
functions of Hamiltonian Ĥ corresponding to the particular energy eigenvalues. The solution of equation (3)
therefore consists of finding the eigenfunctions of Ĥ. Such a problem is called eigenvalue problem. The operator Ĥ
is Hermitian and must therefore have real equation that is what we want; for the energy of the system cannot be
complex or imaginary. If E and E1 are two different eigenvalues Ĥ and 𝜓𝐸 (𝑟⃗) and 𝜓𝐸1 (𝑟⃗) are the numerical
eigenfunctions corresponding to E and E1 respectively.

Then ∫ 𝜓𝐸 (𝑟⃗) 𝜓𝐸1 (𝑟⃗)𝑑 3 𝑟 = ∫ 𝐸𝐸1= constant value

The functions 𝜓𝐸 (𝑟⃗) are said to describe the steady-states of the quantum mechanical system.

Infinite wire

Capacitor without edges

The Step Potential (Energy Less Than step Height)

This potential changes in value in going from one range. Of course potentials which change abruptly (ie continuous
function of 𝑥 ) do not really exist in nature. Nevertheless, these idealised potentials are used frequently in quantum
2
mechanics to approximate real situations because, being constant in each range, they are easy to treat mathematically.
The results we obtain for these potentials will allow us to illustrate a number of characteristic quantum mechanical
phenomena. An analogy, that is surely familiar to students is found in the procedure used in studying
electromagnetism. This involves treating many idealized systems like the infinite wire, the capacitor without edges
etc. These systems are studied because they are relatively easy to handle because they are excellent approximations
to real ones and because real systems are usually complicated to treat mathematically since they have complicated
geometries.

The simplest care is the step potential:

𝑉
𝑉(𝑥) = { 0 𝑥>0 where V0= constant
0
𝑥<0
Example:
Illustrating a physical system with a potential energy function that can be approximated to a step potential. A
charge particle moves along the axis of two cylindrical electrodes held at different voltages. Its potential energy is
constant when it is inside either electrodes but it changes very rapidly when passing from one to the other.

To determine the motion of the particle according to quantum mechanics, we must find a wave function which is a
solution of total Energy E< 𝑉0 , The Schrödinger equation for a step potential. Since this potential is independent
of time, the actual problem is to solve the time-independent Schrodinger equation.
For 𝑥 < 0 (left of the step) 𝑉𝑋 = 0,
So the eigenfunction that will tell us about the behaviour of the particle is a solution to simple TISE.

−ћ2 𝑑 2 𝜓 (𝑥)
= 𝐸𝜓(𝑥)………………………………………………..(1)
2𝑚 𝑑𝑥 2

𝑥 > 0 (right of the step) 𝑉(𝑋) = 𝑉0

We have

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−ћ2 𝑑 2 𝜓 (𝑥)
+ 𝑉0 𝜓(𝑥) = 𝐸𝜓(𝑥) …………………………………….(2)
2𝑚 𝑑𝑥 2

The two equations are solved separately and then an eigenfunction valid for the entire range of x is constructed by
joining the two solutions together at 𝑥 = 0 in such a way to satisfy the requirements.
We assume the solution (general solution traveling wave eigenfunction).

𝜓(𝑥) = 𝐴𝑒 −𝑖𝑘1 𝑥 + 𝐵𝑒 −𝑖𝑘1𝑥 ………………………………………(3)

√2𝑚𝐸
Where 𝑘1 = x< 0 A and B are constants.
ћ

For 𝑉(𝑋) = 𝑉0 and 𝐸 < 𝑉0 we assume a decrease in exponential function

𝜓(𝑥) = 𝑒 −𝑘2𝑥 𝑥 => 0

−ћ2 𝑑 2 𝜓 (𝑥)
+ (𝑉0 − 𝐸)𝜓(𝑥) = 0
2𝑚 𝑑𝑥 2
𝑑 2 𝜓(𝑥) 2𝑚(𝑉0 − 𝐸)𝜓(𝑥)
=
𝑑𝑥 2 ћ2
2𝑚(𝑉0 −𝐸) √2𝑚(𝑉0 −𝐸)
Let 𝑘22 = …………………………………………….(4) 𝑘2 =
ћ2 ћ

We also assume a solution

√2𝑚(𝑉0 −𝐸)
𝜓(𝑥) = 𝐶𝑒 𝑘2𝑥 + 𝐷𝑒 −𝑘2𝑥 ………………………………….(5) where 𝑘2 =
ћ
C=0
𝐶𝑒𝑘2𝑥 generally increases without limit that 𝑥 → +∞

∴ equation (5) becomes

𝜓(𝑥) = 𝐷𝑒 −𝑘2𝑥
𝑑𝜓
At point 𝑥 = 0 the two forms of 𝜓(𝑥) and must be continuous
𝑑𝑥

∴ 𝐷(𝑒 −𝑖𝑘2 𝑥 ) = 𝐴(𝑒 𝑖𝑘1 𝑥 ) + 𝐵(𝑒 −𝑖𝑘1 𝑥 )

∴𝐷 =𝐴+𝐵

For a continuous derivative,

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 𝑑𝜓(𝑥)
= −𝑘2 𝐷𝑒 −𝑘2𝑥
𝑑𝑥
And
𝑑𝜓(𝑥)
= 𝑖𝑘1 𝐴𝑒 𝑖𝑘1𝑥 − 𝑖𝑘1 𝐵𝑒 −𝑖𝑘1 𝑥
𝑑𝑥
At 𝑥 = 0
−𝑘2 𝐷(𝑒 −𝑖𝑘2 𝑥 ) = 𝑖𝑘1 𝐴(𝑒 𝑖𝑘1𝑥 ) − 𝑖𝑘1 𝐵(𝑒 −𝑖𝑘1 𝑥 )
𝑖𝑘2 𝐷
∴ = 𝐴 − 𝐵 …………………………………….(7)
𝑘1
Adding equation. (6) and (7)
𝑖𝑘2
𝐴 = 𝐷⁄2 (1 + ) …………………………………(8)
𝑘1
𝑖𝑘2
𝐵 = 𝐷⁄2 (1 + )
𝑘1
We have now determined A,B and C in terms of D. the eigenfunction for the step potential and energy ECV0 is
given by;
𝐷⁄ (1 + 𝑖𝑘2⁄ ) 𝑒 𝑖𝑘1 𝑥 + 𝐷⁄ (1 − 𝑖𝑘2⁄ ) 𝑒 −𝑖𝑘1𝑥
𝜓(𝑥) = { 2 𝑘1 2 𝑘1 …………………. (9)
−𝑖𝑘2 𝑥
𝐷𝑒
𝑥 ≤ 0, 𝑥 ≥ 0
The remaining arbitrary constant, D, determines the amplitude of the equation.
−𝑖𝐸𝑡
⁄ћ −𝐸𝑡⁄
𝜓(𝑥, 𝑡) = 𝐴𝑒 𝑖𝑘1 𝑥 𝑒 + 𝐵𝑒 −𝑖𝑘1 𝑥 𝑒 −𝑖𝑘1 𝑥 𝑒 ћ
𝑡
𝐷𝑒 −𝑘2𝑥 𝑒 𝑖𝐸 ⁄ћ
𝑡 𝑖(−𝑘1 𝑥−𝐸𝑡⁄ћ)
𝑖(𝑘1 𝑥−𝐸 ⁄ћ)+𝐵
={𝐴𝑒 𝑡
𝑥≤0 for 𝑥 < 0
𝐷𝑒 −(𝑘2𝑥+𝐸 ⁄ћ) 𝑥≥0

First term is the wave travelling in the increasing x direction and the second term is the wave traveling in decreasing
x direction (ie 𝑥 ≤ 0) . We associate this first term with incidence of the particle and the second term reflection of the
particle.

We now use this association to calculate the probability that the incidence of the particle is reflected which we call
the reflection coefficient R. R depends on the ratio 𝐵⁄𝐴 which specifies the amplitude of the reflected part of the wave
functionrelative to the amplitude of the incident part. But in Quantum mechanics probabilities depend on intensities
such as B*B and A*A not an amplitude.
B∗B
Thus 𝑅 = A∗A

B∗B (1 − 𝑖 𝑘2 ⁄𝑘1 )∗ (1 − 𝑖 𝑘2 ⁄𝑘1 )

𝑅= =
A∗A (1 + 𝑖 𝑘2 ⁄𝑘1 )∗ (1 + 𝑖 𝑘2 ⁄𝑘1 )

5
 (1 − 𝑖 𝑘2 ⁄𝑘1 )∗ (1 − 𝑖 𝑘2 ⁄𝑘1 )
𝑅= =1
(1 + 𝑖 𝑘2 ⁄𝑘1 )∗ (1 + 𝑖 𝑘2 ⁄𝑘1 )

The fact that the ratio equals one (1) means that any particle which incidents on the potential step with total energy
less than the height of the step has probability one of being reflected. It is always reflected, this is in agreement
with the predictions of classical mechanics.

SIMPLE HARMONIC OSCILATION

The simple harmonic oscillation is of much importance in physics and all fields based on physics. It is a protype of
any system involving oscillation. It is used to study the vibration of atoms in diatomic molecules the acoustic and
thermal properties of solids which arise from atomic vibrations, magnetic properties of solids that involve
vibrations in the orientation of the nuclei.

SHM is used to describe almost any system in which an entity is executing small vibrations about a point of stable
equilibrium. Application in molecular spectroscopy, solid state physics, nuclear structure, quantum field theory,
quantum optics, quantum statistical mechanics and so forth.

A particle of mass m in one-dimensional harmonic oscillation is subjected to a potential

1
𝑉(𝑥) = 𝑚𝑤 2 𝑥 2 …………………………..(1)
2

𝑘
But 𝑤 =√ in classical mechanics 𝑤 = 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝑘 = 𝑠𝑝𝑟𝑖𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 the
𝑚
resistivity force 𝐹 (𝑥 ) = −𝑘𝑥 …………………(2)
But force 𝐹 = 𝑚𝑎 𝑎 = 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛
𝑑2 𝑥
∴ 𝑚 2 = −𝑘𝑥
𝑑𝑡
6
𝑑2 𝑥 𝑘
= −( )𝑥 𝑘 = 𝑤2𝑚
𝑑𝑡 2 𝑚

A particle of mass m subject to a linear restoring force 𝐹 (𝑥 ) = −𝑘𝑥, k is a force constant.

The total energy of the Harmonic oscillator is given by the Hamiltonian

𝐻 =𝑇+𝑉

𝑃2 1 2
= + 𝑘𝑥
2𝑚 2
𝑃2 1
= + 𝑚𝑤 2 𝑥 2
2𝑚 2
X and P are operators and are Hermitian

We now define two non-Hermitian operators

𝑚𝑤 𝑖𝑝
𝑎=√ (𝑥 + )
ћ 𝑚𝑤

𝑚𝑤 𝑖𝑝
𝑎+ = √ (𝑥 − )
2ћ 𝑚𝑤

Which are known as the annihilation (lowering) and creation (raising) operators respectively

The commutation relation between them is given by

𝑖
[𝑎, 𝑎+ ] = 2ћ (𝑖[𝑥, 𝑝] + 𝑖[𝑝, 𝑥]) = 1

We also define the number operator

𝑁 = 𝑎+ 𝑎

Which is also Hermitian. It can be shown that

𝑚𝑤 2 𝑝2 𝑖
𝑎+ 𝑎 = (𝑥 + ) + ( ) [𝑥, 𝑝]
2ћ 𝑚2 𝑤 2 2ћ

And

𝐻 1
𝑁= −
ћ𝑤 2
7
 𝐻 1
=𝑁+
ћ𝑤 2
1
𝐻 = ћ𝑤 (𝑁 + ) 4
2

Because H is just a linear function of N, N can be diagonalized simultaneously with H. we denote an energy
eigenket of N by its eigenvalue n, so

N|n >= 𝑛 |n > but n is nonnegative integer and from (4)

H|n >= (𝑛 + 1⁄2)ћ𝑤 |n > and the energy eigenvalues are given by

𝐸𝑛 = (𝑛 + 1⁄2)ћ𝑤 [𝑎, 𝑎+ ] = 1

Let us show the physical significant of 𝑎, 𝑎 + and N.

[𝑁, 𝑎] = [𝑎+ 𝑎, 𝑎] = 𝑎+ [𝑎, 𝑎] + [𝑎+ , 𝑎]𝑎 = −𝑎

And [𝑁, 𝑎 + ] = 𝑎+
As a result we have

𝑁𝑎+ ln > = ([𝑁, 𝑎] + 𝑎+ 𝑁) ln >

= (𝑛 + 1)𝑎+ ln >
N𝑎 ln >= ([𝑁, 𝑎] + 𝑎𝑁) ln >
= (𝑛 − 1)𝑎 ln >…………………..(5)
Thus the relation implies that 𝑎 + ln > (𝑎 ln >) is also an eigenket of N with eigenvalue increased (decreased)
by one. Because the increase (decrease) of n by one amount to the creation (annihilation) of one quantum unit of
energy ћw, the term creation operation (annihilation) operator for 𝑎+ (𝑎 ) is decreased appropriately. From
equation (5) it implies that 𝑎 ln
− 1 > are the same up to a multiplicative constant.we write 𝑎 ln > =
𝑐 ln −1 > where c is a numerical constant to be determined from the fact that both ln > and ln − 1 >
normalised.

8
First we note that

< 𝑛|𝑎∗ 𝑎|𝑛 >= |𝑐 2 | 6

We can evaluate the left hand side of equation (6) by noting that 𝑎 + 𝑎 is just the number operator so

𝑛 = |𝑐|2
If c is real and positive by convention then we obtain

𝑎 ln > = √𝑛𝑙𝑛 − 1 > 7

Similarly;

𝑎+ ln > = √𝑛 + 1|𝑛 + 1 >

Suppose we keep on apply the annihilation operator 𝑎 to both sides of (7) we have

𝑎|𝑛 >= √𝑛|n-1>

𝑎2 |𝑛 >= √𝑛(𝑛 − 1) |n-2>

𝑎3 |𝑛 >= √𝑛(𝑛 − 1)(𝑛 − 2) |n-3>

We have

𝑛 =< 𝑛|𝑁|𝑛 >= (< 𝑛|𝑎∗ ). (𝑎|𝑛 >) ≥ 0

Which implies that n can never be negative therefore we conclude that the sequence must terminate with n=0 and
allowed values of n are non-negative. The smallest possible value of n=0 the ground state of the harmonic oscillator
has 𝐸0 = 1⁄2 ћ𝑤

We thus now apply the creation 𝑎 + to the ground state |0 > using 𝑎+ |𝑛 >= √𝑛 + 1|𝑛 + 1 > we obtain

|1 >= 𝑎+ |0 >

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 𝑎+ (𝑎+ )2
|2 >= ( ) |1 >= [ ]|0 >
√2 √2

𝑎+ (𝑎+ )3
|3 >= ( )| 2 >= [ ] |0 >
√3 √3!
(𝑎+ )𝑛
|𝑛 >= [ ]|0>
√𝑛!

We succeeded in constructing simultaneous eigenkets of N and H with eigenvalue 𝐸𝑛 = (𝑛 + 1⁄2)ћ𝑤,

n=0,1,2,3…

Step I potential (Energy Greater than Height)

Example:

An electron in the cathode of photoelectric cell, which has received energy as a result of absorption of photon and
it is trying to escape from the surface of the metallic cathode. If the energy of the electron is not much higher than
the height of the potential step in the potential that it feels at the surface of the metal it may reflect back and would
not be able to escape.

A particle motion under the influence of a step potential is given by

10
 𝑡⁄
𝜓(𝑥, 𝑡) = 𝜓(𝑥 )𝑒 −𝑖𝐸 ℎ

𝜓(𝑥 ) satisfies TISE

The potential is different in the regions and left and right of the step potential.

−ћ2 𝜓(𝑥)
𝑑2 = 𝐸𝜓(𝑥 )………………………… (1) 𝑥<0
2𝑚 𝑑𝑥 2

−ћ2 𝜓(𝑥)
𝑑2 = (𝐸 − 𝑉0 )𝜓(𝑥 )…………………………(2) 𝑥 > 0
2𝑚 𝑑𝑥 2

For free particle of momentum ρ1, the solution of equation (1) is given by 𝜓(𝑥 ) = 𝐴𝑒 𝑖𝑘1 +
𝐵𝑒 −𝑖𝑘1 ……………………(3) 𝑥 < 0

√2𝑚𝐸 p1
𝑘1 = =
ћ ћ
Eqn.(2) also describes the motion of a free particle of momentum 𝑝2 , the general solution is given by

𝜓(𝑥 ) = 𝐶𝑒 𝑖𝑘2 𝑥 + 𝐷𝑒 −𝑖𝑘2 𝑥 ……………….. (4)

√2𝑚(𝐸−𝑉0 ) ρ2
𝑘2 = = …………………….(5) 𝐸 > 𝑉0
ћ ћ

We know that there is only transmitted wave that travels in the region 𝑥 > 0 and there is nothing to cause
𝑑𝜓(𝑥)
reflection so 𝐷 = 0. A, B and C which are constants must be chosen such that 𝜓(𝑥 ) and are continuous
𝑑(𝑥)
at 𝑥 = 0,

Therefore 𝐴(𝑒 𝑖𝑘1 𝑥 ) + 𝐵(𝑒 −𝑖𝑘1 𝑥 )𝑥=0 = 𝐶(𝑒 𝑖𝑘2 𝑥 )𝑥=0

𝑥=0

∴ 𝐴 + 𝐵 = 𝐶 …………………………….(6)
The derivatives should also be satisfied for 𝜓(𝑥 ) at the same 𝑥 = 0

𝑖𝑘1 𝐴(𝑒 𝑖𝑘1 𝑥 )𝑥=0 − 𝑖𝑘1 𝐵(𝑒 −𝑖𝑘1 𝑥 )𝑥=0 = 𝑖𝑘2 𝐶(𝑒 𝑖𝑘1 𝑥 )𝑥=0

11
𝑘1 (𝐴 − 𝐵) = 𝑘2 𝐶 ……………………..(7)
From (6) and (7)

𝑘1 −𝑘2 2𝑘1
𝐵= 𝐴 and 𝐶 = 𝐴
𝑘1 +𝑘2 𝑘1 +𝑘2

It is not necessary to evaluate A that determines the amplitude of the eigen function. The reflection coefficient is
defined as :

𝐵∗ 𝐵 𝑘1 −𝑘2 𝑘1 −𝑘2 𝑘1 −𝑘2 2

𝑅= =( )( )=( ) ………………………….. (8) 𝐸 > 𝑉0
𝐴∗ 𝐴 𝑘1 +𝑘2 𝑘1 +𝑘2 𝑘1 +𝑘2

From the above equation 𝑅 < 1 when 𝐸 > 𝑉0 ie whether the total energy is greater than the height of the
potential step and this in contrast to 𝑅 = 1 when 𝐸 < 𝑉0

We now want to define the transmission coefficient T which specifies the probability that a particle will be
transmitted past the potential step from the region 𝑥>0
The expression for transmission coefficient T is slightly different from R because the velocity in the two regions is
different.

Transmission and reflection coefficients are actually defined in terms of the ratio of the probability fluxes. A
probability flux is defined as the probability per second that a particle will be found crossing some reference point
traveling in a particular direction.

𝑉1 𝐵∗ 𝐵 𝐵∗ 𝐵
Thus 𝑅 = = =VELOCITY OF PARTICLE IN REGION 𝑥<0
𝑉1 𝐴∗ 𝐴 𝐴∗ 𝐴

𝑉2 𝐶 ∗ 𝐶 𝑉2 2𝑘1 2
𝑇= = ( ) V2=VELOCITY OF PARTICLE IN REGION 𝑥>0
𝑉1 𝐴∗ 𝐴 𝑉1 𝑘1 𝑘2

𝜌1 ћ𝑘1 𝜌2 ћ𝑘2
𝑉1 = = and 𝑉2 = =
𝑚 𝑚 𝑚 𝑚

∴ T is given by
𝑘2 (2𝑘1 )2 4𝑘1 𝑘2
𝑇= = (𝑘 2 ……………………. (9) 𝐸 > 𝑉0
𝑘1 (𝑘1 +𝑘2 )2 1 +𝑘2 )

It can be shown from (8) and (9) that:

12
 𝑅+𝑇 =1 (10)
This is the reason why the reflection and transmission coefficients were defined in terms of the probability fluxes.

Thus when the probability flux incident upon the potential step, it is split into a transmitted flux and reflected flux,
and absorbance in this case equals zero and their sum equals incident flux. The probability of the particle either
transmitted or reflected equals one. From equation (10), we can say that when the particle’s flux incidents on the
potential step, it does not vanish nor does the particle itself split at the step. In a particle experiment the particle will
go one way or the other. For large number of experiments the probability of going in decreasing x direction is
measured by R and going in increasing x direction is determined by T. A reflection and transmission coefficient for
particle incident upon a potential step.

2
𝑉
1−√1− 0⁄𝐸 𝐸
𝑅 =1−𝑇 =( ) >1
𝑉 𝑉0
1+√1− 0⁄𝐸

Fig. The reflection and transmission coefficient R and T for a particle incident upon a potential step.

EXAMPLE:

When a neutron enters a nucleus, it experiences a potential energy which drops at the nuclear surface very rapidly
from a constant internal value of about V=-50MeV.The decrease in potential is what makes it possible for a neutron
to be bound in a nucleus. Consider a neutron incident with incident with external kinetic energy of V=5MeV, which
is typical for a neutron that has just been emitted form a nuclear fusion. Estimate the probability that the neutron
will be reflected at the nuclear surface, thereby failing to enter and have its chance at inducing another fusion.

Soln.

Neutron –nuclear potential to be 1-D step potential.

13
 2
1−√1−50⁄55
V0=50MeV E=55MeV R=( ) = 0.29
1−√1−50⁄55

Particle of energy E,1-D. dimensional rect po base mass m, incident wave of amplitude A=1 and transmitted wave
of amplitude F. for a particle of energy 𝐸 < 𝑉0 , the solution function in region (1) and (2) contains right and left
propagation.

in region 1.

𝜓, (𝑥 ) = 𝐴𝑒 𝑖𝑘1 𝑥 + 𝐷𝑒 −𝑘1 𝑥

𝑘2 = √2𝑚𝐸⁄ћ

Region (2).

2𝑚(𝑉0 − 𝐸 )⁄
𝜓2 (𝑥 ) = 𝐴𝑒 𝑖𝑘1 𝑥 + 𝐷𝑒 −𝑘2 𝑥 where 𝑘2 = √ ћ
Note that the particle wave function has left & right propagation exponentially decaying solution. This is required if
a tunneling will flow through the barrier.

Because we will be considering a right particle incident from the left in region 3, we needed only to consider a right
propagating wave. Boundary conditions (wave function and its derivation)

A+B= C+D……………….(1)

𝑖𝑘2
(𝐴 − 𝐵) = (𝐷 − 𝐶 )………………………… (2)
𝑘1

𝐶𝑒 𝑘2 𝐿 + 𝐷𝑒 −𝑘2 𝐿 = 𝐹𝑒 𝑖𝑘1 𝐿 ………………………. (3)

14
 𝑖𝑘
𝐶𝑒 𝑘2 𝐿 − 𝐷𝑒 −𝑘2 𝐿 = 𝐹𝑒 𝑖𝑘𝐿 ……………………… (4)
𝑘2

2
Since tunneling transmission probability is |𝐹⁄
𝐴| , we eliminate other coefficients.

Adding (1) and (2) gives

𝑖𝑘2 𝑖𝑘2
2A= (1 − ) 𝐶 + (1 + ) 𝐷 …………………………..(5)
𝑘1 𝑘1

Adding (3) and (4)

𝑖𝑘
2𝐶𝑘2 𝐿 = (1 + ) 𝐹𝑒 𝑖𝑘𝐿 …………………………………… (6)
𝑘2

(3)- (4)

𝑖𝑘1
2D𝑒 −𝑘2 𝐿 = (1 + ) 𝐹𝑒 𝑖𝑘𝐿 ………………………………….( 7)
𝑘2

Using eqn. (6) and (7) to eliminate C and D from equation (5) gives;

𝑖𝑘2 𝑖𝑘 𝑖𝑘 𝑖𝑘
2𝐴 = (1 − ) (1 + ) 𝐹⁄ 𝑖𝑘1 𝐿−𝑘2 𝐿 + (1 + ) (1 − ) 𝐹⁄ 𝑖𝑘1 𝐿+𝑘2 𝐿
𝑘1 𝑘2 2𝑒 𝑘 𝑘2 2𝑒

𝐹 4𝑘1 𝑘2 𝑒 −𝑖𝑘1 𝐿
= (𝑘−𝑖𝑘2 )(𝑘2 +𝑖𝑘2 )𝑒 −𝑘2 𝐿 +(𝑘+𝑖𝑘2 )(𝑘2 +𝑖𝑘)𝑒 𝑘2 𝐿
……………………. (8)
𝐴

𝐹 4𝑖𝑘1 𝑘2
= 2 ………………………………………. (9)
𝐴 −(𝑘2 −𝑖𝑘⁄𝑘 ) +(𝑘2 +𝑖𝑘2 )2 𝑒 −𝑘2 𝐿
2

Dividing through (9) by (𝑘2 )2 gives;

15
𝐹 4𝑖𝑘1 |𝑘2
= *𝑒 −𝑘1 𝐿 ……………………………. (10)
𝐴 −(1−𝑖𝑘/𝑘2 )2 +(1+𝑖𝑘1 /𝑘2 )2 𝑒 −𝑘2 𝐿

Magnitude of equation (10) square

2
𝐹∗ 𝐹 16(𝑘1 |𝑘2 )
= 2 2 4 ……………(11)
𝐴∗ 𝐴 𝑖𝑘 𝑖𝑘 𝑖𝑘
(1+ 1⁄𝑘 ) (1+ 1⁄𝑘 ) (𝑒 −2𝑘2 𝐿 +𝑒 2𝑘2 𝐿 )−(1+𝑖𝑘𝑘 )4 (1+ 1⁄𝑘 )
2 2 2

𝐹 2 16(𝑘1 ⁄𝑘2 )2
| | = 4 4 ………….. (12)
𝐴 (1+𝑖𝑘1 ⁄𝑘2 )2 (1+𝑖𝑘1 ⁄𝑘2 )2 ((𝑒 −𝑘2 𝐿 −𝑒 𝑘2 𝐿 )+2)`−(1−𝑖𝑘1⁄𝑘 ) −(1+𝑖𝑘1⁄𝑘 )
2 2

𝐹 2 16(𝑘1 /𝑘2 )2
| | = 4 4 ……………………..(13)
𝐴 (1+𝑖𝑘1 /𝑖𝑘2 )2 −(4𝑠𝑖𝑛ℎ2 (𝑘2 𝐿)+2)−(1−𝑖𝑘1⁄𝑘 ) −(1+𝑖𝑘1⁄𝑘 )
2 2

Dealing with the last two terms in parenthesis in the denominator, it is easy to check that

4 4 2
𝑖𝑘1 𝑖𝑘1 ( ⁄ )2 𝑖𝑘1
(1 − ⁄𝑘 ) + (1 + ⁄𝑘 ) = −16 𝑘1 𝑘2 + 2 (1 + ⁄𝑘 ) … …. …….. (14)
2 2 2

Substituting (14) into (13)

𝐹 2 (𝑘1 /𝑘2 )2
| | =1 2 ……………………….. (15)
𝐴 ((1+𝑖𝑘1 ⁄𝑘2 )2 (1−𝑖𝑘1 ⁄𝑘2 )2 )𝑠𝑖𝑛ℎ2 (𝑘2 𝐿)+(𝑘1⁄𝑘 )
4 2

𝑘1 /𝑘2
=1 …………………………………… (16)
(1+(𝑘1 ⁄𝑘2 )2 )2 𝑠𝑖𝑛ℎ2 (𝑘2 𝐿)+(𝑘1 ⁄𝑘2 )2
4

So the tunneling transmission probability is

𝐹 2 1
| | = 2 …………………………………….(17)
𝐴 𝑘21 +𝑘2
2
1+( 2𝑘 𝑘 ) 𝑠𝑖𝑛ℎ2 (𝑘2 𝐿)
1 2

16
Particle in an Infinite Deep Square Well Potential

∞ ∞

X
X=𝑙
X=0
0 0<𝑥<𝑙
𝑈(𝑥) = {
∞ 𝑥 < 0, 𝑥 > 𝑙
17
For the region 0 < 𝑥 < 𝑙, 𝑈(𝑥) = 0

The solution is

ѱ(𝑥) = 𝐴 sin 𝑘𝑥 + 𝐵𝑐𝑜𝑠 𝑘𝑥 1

2𝑚𝐸
𝑘=√ 2 2
ћ

Outside the well 𝑈(𝑥) = ∞ 𝑠𝑜 ѱ(𝑥) = 0

Wavefunction must be continuous, hence if ѱ(𝑥) = 0 outside the well, it must be zero at 𝑥 = 0 and 𝑥 = 𝑙 and
ѱ(𝑥) = 0 𝑎𝑛𝑑 ѱ(𝑙) = 0

The condition at 𝑥 = 0, since 𝑠𝑖𝑛 𝑘𝑥 = 0 but 𝑐𝑜𝑠𝑘𝑥 = 1

∴ 𝐴𝑠𝑖𝑛(0) + 𝐵𝑐𝑜𝑠(0) = 0 𝑎𝑛𝑑 𝐵 = 0

Equation 1 now becomes

ѱ(𝑥) = 𝐴𝑠𝑖𝑛𝑘𝑥

Considering the boundary conditions

ѱ = 0 𝑎𝑡 𝑥 = 𝑙

0 = ѱ(𝑙) = 𝐴𝑠𝑖𝑛𝑘𝑙

𝑠𝑖𝑛𝑘𝑙 = 0

The sine is zero for angles 0, 𝜋, 2𝜋, 3𝜋, … and thus

𝑘𝑙 = 𝑛𝜋 𝑛 = 1, 2, 3, … 𝜋
𝑛𝜋
𝑘=
𝑙

2𝑚𝐸 𝑛𝜋 2𝑚𝐸
But 𝑘 = √ 𝑎𝑛𝑑 =√ squaring both sides gives
ћ2 𝑙 ћ2

𝑛2 𝜋 2 2𝑚𝐸
= 2
𝑙2 ћ
𝑛2 ℎ2
𝐸= 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, …
8𝑚𝑙 2

18
A particle trapped in a rigid box thus can only have certain quantized energies.

For 𝑛 = 1

ℎ2
𝐸1 =
8𝑚𝑙 2
4ℎ2
𝐸2 = = 4𝐸1
8𝑚𝑙 2
9ℎ2
𝐸3 = = 9𝐸1
8𝑚𝑙 2
𝐸𝑛 = 𝑛2 𝐸1

∞ ∞

𝐸3 = 9𝐸1

𝐸2 = 4𝐸1

𝐸1

19
𝐸1 is the zero-point energy. At absolute zero (0K), quantum mechanics predicts that the particle in a box would not
ћ𝜋
rest but would have a zero-point energy. Also 𝑝1 = ћ𝑘 = , the smaller the width the larger the momentum (and
𝑙
energy).
𝑛𝜋
The wave function ѱ = 𝐴𝑠𝑖𝑛𝑘𝑥 for each of the quantum states is (since 𝑘 = )
𝑙

𝑛𝜋
ѱ𝑛 = 𝐴𝑠𝑖𝑛 𝑥)
𝑙
𝐴 can be determined using normalization condition
∞
𝑙
𝑛𝜋
1 = ∫ ѱ 𝑑𝑥 = ∫ 𝐴2 𝑠𝑖𝑛2 ( 𝑥) 𝑑𝑥
2
0 𝑙
−∞

The integral is equal to

𝐴2 2
1= 𝑙=𝐴=√
2 𝑙

2 𝑛𝜋
ѱ𝑛 = √ sin( 𝑥)
𝑙 𝑙

20
The Figures above show the wave function and probability function for n=1, 2, 3, …,10 for a particle in a box
(Courtesy Giancoli).

Question

An electron is trapped in an infinitely deep square well potential of length 𝑙 = 1.0 × 10−10 𝑚.

i) Calculate the three lowest energy levels.

ii) If a photon were emitted when an electron jumps from the 𝑛 = 2 state to 𝑛 = 1 state, what would be its
wavelength?

Solution

i) In the ground state 𝑛 = 1

ℎ2 (6.63 × 10−34 )2
𝐸= = = 6.03 × 10−18 𝐽
8𝑚𝑙 2 8(9.11 × 10−31) (1.0 × 10−10 )2

21
 6.03 × 10−34
𝐸1 = = 37.7 𝑒𝑉
1.60 × 10−19
𝐸2 = 22 𝐸1 = 150.8 𝑒𝑉

𝐸3 = 32 𝐸1 = 339.3 𝑒𝑉

ii) 𝐸2 − 𝐸1 = 150.8 − 37.7 = 113.1 𝑒𝑉

1240 1240
𝜆 (𝑛𝑚) = = = 9.31 𝑛𝑚
𝐸(𝑒𝑉) 113.1

Tunneling through a Barrier

In quantum mechanics, a particle such as an electron can penetrate a barrier into region forbidden by classical
mechanics. There are a number of applications that would be discussed later.

Consider a particle of mass 𝑚 and energy 𝐸 traveling to right of the 𝑥 axis in a free space where the potential is
𝑈 = 0 so the energy is all kinetic (𝐸 = 𝐾). The particle encounters a narrow potential barrier of height 𝑈0 (in
energy units) is greater than 𝐸 and thickness 𝑙 (distance units).

22
Since 𝐸 < 𝑈0 , we expect from classical mechanics that the particle cannot penetrate the barrier, but it would simply
be reflected and would return in the opposite direction. This happens to macroscopic objects. Quantum mechanics
predicts non-zero probability for finding the particle on the other side of the barrier.

The particle approaches with a sinusoidal wave but within the potential it is an exponential decay. However, the
exponential decay dies away to zero, at the end of the barrier (𝑥 = 𝑙) and 𝑥 > 𝑙 there is again a sinusoidal wave
function.

But it is a sine wave of greatly reduced amplitude. Since |ѱ|2 is non-zero beyond the barrier that is a non-zero
probability that the particle penetrates the barrier. The process is called tunneling through a barrier or barrier
penetration.

We describe the tunneling probability with transmission coefficient 𝑇 and reflection coefficient 𝑅. If 𝑇 = 0.04 then
𝑅 = 0.96. Note that 𝑇 + 𝑅 = 1 since an incident particle must either reflect or tunnel through. The transmission
coefficient can be defined as

𝑇 = 𝑒 −2𝐺𝑙

For 𝑇 ≪ 1 and

2𝑚(𝑈0 − 𝐸)
𝐺=√
ћ2

Question

A 50 𝑒𝑉 electron approaches a square barrier 70 𝑒𝑉 high and

i) 1.0 𝑛𝑚 thick
ii) 0.10 𝑛𝑚 thick
What is the probability that the electron will tunnel through?

Solution

i)

𝑈0 − 𝐸 = (70 − 50) × (1.6 × 10−19 )

= 3.2 × 10−18 𝐽

2(9.1 × 10−31 ) × (3.2 × 10−18 ) × (1.0 × 10−9 )

2𝐺𝑙 = 2 √ = 46
1.055 × 10−34

23
 𝑇 = 𝑒 −2𝐺𝑙 = 𝑒 −46 = 1 × 10−20

iii) For
𝑙 = 0.10 𝑛𝑚, 2𝐺𝑙 = 4.6 𝑇 = 𝑒 −4.6
0.010 %
= 1.0 % chance of penetration
Examples of application of tunneling
i) Tunnel diode
ii) Scanning tunneling microscope
iii) Radioactive decay
iv) Atomic force microscope

Superconductors and Tunneling

Superconductors are metals and semiconductors which when current flows through them behave as if
there is no resistance to the flow of current at very low temperatures. When you plot a graph of resistance
against temperature there is an initial drop in resistance as temperature decreases till a point is reached
called the critical temperature or transition temperature where the resistance drops to zero.

The

Angular momentum
⃗⃗ of the
An electron of mass m in a circular Bohr orbit of radius r with a velocity v. The orbital angular momentum 𝐿
eelectron of linear velocity v.

See diagram on board

m= mass of electron

e= charge on electron

Orbital magnetic momemt

24
Dipole moment of electron of mass m, and charge (-e) in a circular pole of radius r, orbiting with a velocity v.

⃗⃗ of the electron with linear velocity V is given by;

The orbital angular momentum 𝐿

𝐿⃗⃗ = 𝑟⃗ 𝑥 𝑝⃗ r= radius of orbit, p=linear momentum

𝐿 = 𝑚𝑣𝑟 (1)

Charge circulating current in the loop generates

𝑖 = 𝑒⁄𝑇 (2)

2𝜋𝑟
But 𝑇 = (3)
𝑣
𝑒𝑣
∴𝑖= (4)
2𝜋𝑟

T= period of charge circulating a loop of magnetic field which is the same at large distance from the loop as at that
of magnetic dipole located at center of the loop and oriented far to the plane.

The orbital magnetic dipole µ𝐿 of the system is given by;

µ𝐿 = 𝑖𝐴 …………………………… (5) A = Area =𝜋𝑟2

𝑒𝑣
µ𝐿 = ∗ 𝜋𝑟 2
2𝜋𝑟
𝑒𝑣𝑟
µ𝐿 = ………………………… (6)
2

Dividing through equation (6) by equation (1)

µ𝐿 𝑒𝑣𝑟 𝑒
= =
𝐿 2𝑚𝑣𝑟 2𝑚

This ratio is a combination of universal constants

µ𝐿 𝑔𝑙 µ𝑏
=
𝐿 ћ

𝑒ћ
Where µ𝑏 =
2𝑚

25
= 0.929× 10−23 𝐴𝑚−2

𝑔𝐿 = 1 and it is called orbital g-factor or gyromagnetic ratio

And µ𝑏 = Bohr magneton

−𝑔𝑙 µ𝑏 𝐿
µ𝑙 = µ𝑙 and L are anti parallel
ћ

But L=√𝑙(𝑙 + 1) ћ 𝑙= the orbital angular momentum quantum number or the orbital quantum
number.

𝑔𝑙 µ𝑏 𝐿 𝑔𝑙 µ𝑏
∴ µ𝐿 = = √𝑙(𝑙 + 1)ћ
ћ ћ

= 𝑔𝑙 µ𝑏 √𝑙(𝑙 + 1)
−𝑔𝑙 µ𝑏 𝑔𝑙 µ𝑏
µ 𝑙2 = 𝐿𝑧 = 𝑚𝑙 ћ
ћ ћ
µ𝐿 = magnetic dipole moment is placed in an applied magnetic field B, it experiences a torque and associated
with this torque is a potential energy of orientation

𝜏 = µ𝐿 𝑋𝐵
∆𝐸 = −µ𝐿 ∗ 𝐵
Stern-Gerlach Experiment
A beam of vaporized silver atoms is collimated and passed through an inhomogeneous magnetic field of magnetic
𝜕𝐵
gradient in the z direction. Before entering the field the beam of silver atoms were randomly oriented. After
𝜕𝑧
entering the field they were split into two, the spin up were parallel to the field and the spin down anti-parallel. The
experiment was repeated for other atoms and two traces were always obtained.

26
 Z
S

oven

N
Collimator

Magnet
Detector/Screen
The diagram showing the Stern-Gerlach Experiment

This results could only be explained by postulating that an electron has an intrinsic (built-in) magnetic dipole
moment µ𝑠 and posses an intrinsic angular momentum S called spin. Spin is purely quantum mechanical concept
and has classical analog.

𝑆 = √𝑠(𝑠 + 1) ћ and Z- component 𝑆𝑍

𝑆𝑧 = 𝑚𝑠 ћ 𝑆𝑥 𝑎𝑛𝑑 𝑆𝑦 are not quantized s is spin quantum number and 𝑚𝑠 is spin magnetic quantum
number

𝑔𝑆 µ𝑏 𝑆⃗
µ𝑠 = −
⃗⃗⃗⃗
ћ
µ𝑆𝑍 = −𝑔𝑆 µ𝑏 𝑚𝑠 𝑔𝑠 = spin g factor

𝑔𝑠 = 2
1
𝑠 is called spin or spin quantum number and has a value of 𝑠 = 2 and 𝑚𝑠 is called spin magnetic quantum
number 𝑚𝑠 = ± 1⁄2

1
𝑚𝑠 = + 2, which is spin up parallel

1
𝑚𝑠 = − 2, which spin down or anti-parallel
27
The transverse force FZ experience the atoms in z direction is given by;

𝜕𝐵 −𝑔µ𝐵 𝑆𝑍
F=µ𝑍 …………(1) But µ𝑍 =
𝜕𝑍 ћ

𝜕𝐵
∴ 𝐹 = 𝑔µ𝐵 𝑚𝑠 SZ=msћ and 𝑔(𝑠) = ±2
𝜕𝑍

𝜕𝐵
∴ 𝐹 = µ𝐵
𝜕𝑍
The experiment of Stern & Gerlach which discovered the existence of spin also found space quantization i.e. the
orientation of atoms in space is quantized and only a set of allowed values are obtained.

Quantum particles may possess an orbital angular momentum and an intrinsic angular momentum called spin. The
orbital angular momentum resembles the classical particle. It is a vector with both magnitude and direction but spin
angular momentum does not have a classical manifestation.

Angular momentum in quantum in quantum physics must be specified using quantum numbers. Normally l and ml
are used to describe orbital angular momentum and s and ms are used for spin angular momentum. Quantum
numbers j and mj are used when quantum numbers arises from a combination of spin and orbital angular moment
and when general angular moment is being described. The only possible precise values for the magnitude of orbital
angular momentum are given by;

L=√𝑙(𝑙 + 1)ћ where l=0,1,2,3,4……

When we choose the orbital angular momentum in the z direction, there are 2l+1 possible outcome given by;

𝐿𝑧 = 𝑚 𝑙 ћ
Total Angular Momentum
Angular momentum can have both orbital and spin angular momenta. For example a 2p state of hydrogen 𝑙 = 1 and
1 1
𝑠 = 2. In the 4d state 𝑙 = 2 and 𝑠 = 2. The total angular momentum is the vector sum of the orbital angular
⃗ and the spin 𝐒⃗:
momentum 𝐋

⃗ + 𝐒⃗
𝐉⃗ = 𝐋

The magnitude of the total angular momentum 𝐉⃗ is quantized

𝐽 = √𝑗(𝑗 + 1) ћ

28
For the single electron in the hydrogen atom quantum mechanics give the result that 𝑗 can be

1
𝑗 =𝑙+𝑠 =𝑙+
2
Or

1
𝑗 =𝑙−𝑠 =𝑙−
2
1
But 𝑗 can never be less than zero, just as 𝑙 and 𝑠. For 1𝑠 state, 𝑙 = 0 and 𝑗 = 2 is only possibility. For 𝑝 states, say
3 1
2𝑝 state, 𝑙 = 1 𝑎𝑛𝑑 𝑗 can be either 𝑜𝑟 2. The 𝑧component for 𝑗 is quantized in the usual way:
2

𝑚𝑗 = +𝑗, 𝑗 − 1, … , 𝑗 + 1, −𝑗

Question

What are the possible values for 𝑗 in the 3𝑑 state of a hydrogen?

Solution

1
𝑗 =𝑙+𝑠 =𝑙+
2
or
1
𝑗 =𝑙−𝑠 =𝑙−
2
For a 𝑑 state 𝑙 = 2

Therefore
1 5
𝑗=𝑙+𝑠 =2+ =
2 2
1 3
𝑗=𝑙+𝑠 =2− =
2 2
5 3
𝑗= ,
2 2

SPECTROSCOPIC NOTATION
The specific state of an atom including the total angular momentum quantum number 𝑗, using the following
spectroscopic notation
29
 𝑛𝐿𝑗

Where 𝐿 is the orbital quantum number

𝐿 = 0 1 2 3 4

𝑙𝑒𝑡𝑡𝑒𝑟 = 𝑆 𝑃 𝐷 𝐹 𝐺
3
Example: 2𝑃3⁄2 has 𝑛 = 2, 𝑙 = 1, 𝑗 = 2

ORBITAL INTERACTION ENERGY

When a magnetic dipole µ ⃗⃗ is placed in a magnetic field exerts a torque 𝜏 = µ × 𝐵 on the dipole. The potential
energy associated with this interaction is given by

𝑈=µ ⃗⃗
⃗⃗. 𝐵

⃗⃗ is directed along the z axis

If the 𝐵
𝑒
⃗⃗ 𝑧 = −
µ 𝐿𝑧 , 𝐿𝑧 = 𝑚𝑙 ћ; 𝑚 = 0, ±1, ±2, … , ±𝑙
2𝑚

𝑒ћ
µ𝑧 = 𝑚
2𝑚 𝑙
The interaction energy is given by

𝑒ћ
𝑈= 𝑚𝐵
2𝑚 𝑙
𝑈 = 𝑚𝑙 µ 𝐵 𝐵

The effect of the magnetic field is to shift the energy of each orbital state by U. The interaction energy depends on
the value of 𝑚𝑙 because 𝑚𝑙 determines the orientation of the orbital magnetic moment relative to the magnetic field.
Without a magnetic field these states have the same energy; that is they are degenerate. The magnetic field removes
the degeneracy. In the presence of magnetic field, they are split into 2𝑙 + 1 distinct energy levels and adjacent
𝑒ћ
energy levels differ in energy by 2𝑚 𝐵 = µ𝐵 𝐵.

30
For a hydrogen
𝑙= 3
n= 4
𝑙= 2
n= 3

𝑙= 1
n= 2

𝑙= 0
n= 1
No magnetic field With magnetic field

Zeeman Effect
It is the splitting of atomic energy levels and the associated spectra when atoms are placed in a magnetic field. This
confirms space quantization

No magnetic field

With a magnetic field

31
One application of Zeeman Effect is splitting of energy levels by a magnetic field which is the basis of magnetic
resonance technique.

2
3d
0

-2
Ei -Ef

2p

Selection Rules
∆𝑙 = ±1
∆𝑚𝑙 = 0, ±1

Spin Orbit interaction

The interaction between electrons spin magnetic dipole moment and the internal magnetic field of the orbiting
electrons in the atom. The internal magnetic field is related to the electrons’ orbital angular momentum. It is a weak
interaction and it is responsible in part for the fine structure of the excited state of one-electron atom.

An analogous effect of spinning orbit interaction occurs in nuclei called nuclear spin-orbit interaction but in such
atoms its reasonable because the internal magnetic fields are strong nucleus of the atom has a magnetic dipole moment
that interacts with the orbital and /or spin magnetic dipole moment of electrons. These effects are called hyperfine
structure radio astronomers use this wavelength to map clouds in interstellar hydrogen gas that are too cold to emit
visible.

32
Larmor Precession
Magnetic moments are not statically aligned exactly parallel or anti-parallel to an external magnetic field. They are
forced to align at angle to the magnetic field B and this causes them to wobble around the axis of the field at a fixed
freq.

Example of this precession “wobble” is a spinning top. It is the spin angular momentum of the top that prevents it
from falling over and causing it to wobble in addition to spinning.

[adakato]

The periodic wobbling mention that the top assumes in a gravitational field is called precession. The Earth also
precesses on its axis but much slower.

In an exactly analogous way, magnetic moment vector of atoms in a magnetic field precesses with a characteristic
frequency called the Larmor frequency 𝑤.

ћ𝑤 = 𝑔𝑙 µ𝐵 𝐵

𝑔𝑙 µ𝐵 𝛽
𝑤=
ћ
Questions

1. Consider an electron in hydrogen having total energy -0.5440 eV.

A) What are the possible values of its orbital angular momentum (in terms of ћ)?
B) What wavelength of light would it take to excite this electron to the next higher
shell? Is this photon visible to humans?
2. A quantum state is four fold degenerate. If 𝑛 = 2 and|𝑛 𝑙 𝑚 > is used. If 𝑛 is the
principal quantum number, 𝑙 orbital quantum number and 𝑚 magnetic
quantum number. Write down the degenerate states.
3. How many different states are possible for an electron whose principal
quantum number is 𝑛 = 3.

33
 Solution
n l ml ms N l ml ms

3 2 2 ½ 3 1 1 1/2

3 2 2 -1/2 3 1 1 -1/2

3 2 1 ½ 3 1 0 1/2

3 2 1 -1/2 3 1 0 -1/2

3 2 0 ½ 3 1 -1 1/2

3 2 0 -1/2 3 1 -1 -1/2

3 2 -1 ½ 3 0 0 1/2

3 2 -1 -1/2 3 0 0 -1/2

3 2 -2 ½

3 2 2 ½

Today, we consider the picture of a spinning electron as not legitimate. We cannot view an electron as localized
object, much less a spinning one. What is important is that the electron can have two different states due to some
1
intrinsic property that behaves like angular momentum called spin. Electron has spin quantum number 𝑠 = 2 which
produces angular momentum

√3
𝑠 = √𝑠(𝑠 + 1)ћ= ћ
2
34
 1 1
The z component 𝑆𝑧 = 𝑚𝑠 ћ and 𝑚𝑠 = 2 , − 2 i.e. spin up and spin down respectively.

Example;

A boson W is spin-one particle with s=1 and ms=+1,0,-1

Electron is spin-half (fermion) with s=1/2 and ms=±1/2

𝐿𝑥 = ypz − Zpy [Lx , Ly ] = iћLZ

𝐿𝑦 = Zpx − Xpy [Ly , LZ ] = iћLx

𝐿𝑍 = xpy − ypx [Lz , Lx ] = iћLy

∂ z∂
𝐿̂𝑥 = −iћ (y − ) [Sx1 , Sy ] = iћSz
∂z ∂y

∂ ∂
𝐿̂𝑦 = −iћ (Z −x ) [Sy , Sz ] = iћSX
∂x ∂z

∂ ∂
𝐿̂𝑥 = −iћ (x −y ) [Sz , Sx ] = iћSy
∂y ∂x

[𝐽+ , 𝐽− ] = 2ћJ+ L2 = LX 2 + Ly 2 + LZ 2

𝐽− J+ = J 2 − JZ2 + ћJZ J 2 = Jx 2 + Jy 2 + Jz 2

𝐽− J+ = J 2 − Jz 2 − ћJz S 2 = Sx 2 + Sy 2 + Sz 2

𝐽4 = Jx + iJy

𝐽− = 𝐽𝑥 − 𝑖𝐽𝑦

𝐿+ = 𝐿𝑥 + 𝑖𝐿𝑦

35
 𝐿− = 𝐿𝑥 − 𝑖𝐿𝑦

𝑆+ = 𝑆𝑥 + 𝑖𝑆𝑦

𝑆− = 𝑆𝑥 − 𝑖𝑆𝑦

[𝐴, 𝐵] = [𝐴𝐵 − 𝐵𝐴]

[𝐴, 𝐵 + 𝐶 ] = [𝐴, 𝐵] + [𝐴, 𝐶 ]
[𝐴, 𝐵 − 𝐶 ] = [𝐴, 𝐵] − [𝐴, 𝐶 ]
[𝐴, 𝐵𝐶 ] = 𝐵[𝐴, 𝐶 ] + [𝐴, 𝐵]𝐶

Example;

Show that:

[𝐽+ , 𝐽𝑦 ] = 𝑖ћ𝐽𝑧 [𝐽2 , 𝐽𝑧 ] = 0

[𝐽𝑧 , 𝐽+ ] = +ћ𝐽+

Orbital Interaction Energy

When a magnetic dipole µ ⃗⃗ is placed in a magnetic field 𝛽⃗ , the field exerts a torque
⃗⃗𝑋𝛽⃗ on the dipole. The potential Energy associated with this interaction is given
𝜏⃗ = µ
⃗⃗. 𝛽⃗
u= µ

If the 𝛽⃗ is directed along the z-axis

−𝑒
µ𝑧 = 𝐿 𝐿𝑧 = 𝑚1 ћ 𝑚 = 0, ±1, +2 𝑡𝑜 ± 𝑙
2𝑚 𝑧

36
 −𝑒 𝑒ћ
µ𝑧 = 𝐿𝑧 = −𝑚𝑙
2𝑚 2𝑚
Interacting Energy
𝑒ћ
µ = −µ𝑧 𝛽 = 𝑚𝑙 𝛽 (orbital magnetic interacting energy)
2𝑚

𝑢𝛽 = 𝑒ћ⁄2𝑚 (Bohr magneton)

µ = 𝑚𝑙 µ𝛽 𝛽 (orbital magnetic interaction)

the effect of the magnetic field is to couple the energy of each orbital state by an
amount U. The interacting energy u depends on the value of the orbital magnetic
moment relative to the magnetic field 𝑚𝑙 is the magnetic quantum number.

𝑚𝑙 = (2𝑙 + 1) 𝑙 = 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 𝑚𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑞𝑢𝑎𝑛𝑡𝑢𝑚 𝑛𝑢𝑚𝑏𝑒𝑟

Without a magnetic field these states have the same energy; that is they are
degenerated. The magnetic field removes the degeneracy. In the presence of
magnetic field they are split into 2𝑙 + 1 distinct energy levels; adjacent energy levels
differ in energy by (𝑒ћ⁄2𝑚)𝛽 = µ𝛽 𝛽.

For hydrogen:

The Zeeman effect.

37
It is the splitting of atomic energy levels and the associated (spectrum lines(spectra))
when the atoms are placed in a magnetic field. This effect confirms experimentally
the quantization of angular momentum.

One application of Zeeman effect is the splitting of energy levels by a magnetic field
which is the basics of magnetic resonance techniques.

Splitting of the energy levels of d state (l=2) caused by an external magnetic field,
assuming only an orbital magnetic moment.

Selecting rules

∆𝑙 = ±1
∆𝑚𝑙 = 0, ±1
Spin-orbit interaction

Show that [𝐽2 , 𝐽𝑍 ] = 0 light.

38
A particle has orbital angular momentum given by the quantum number 𝑙 = 3 and
1
spin angular momentum given by the quantum number 𝑠 = .
2

a) How many distinct states are there with different values for z components of
the orbital and spin angular moments?
b) What are the possible values for the quantum number j that describes the total
angular momentum of the particle?
c) How many distinct states are there with different values for the magnitude and
z component of total angular momentum?

A chemical electron moves in a circle of radius 1mm with velocity 1ms-1.

What is the value of the quantum number which gives a quantized angular
moment close to the angular momentum of the classical electron?

Angular Momentum and Commutations and Eigenvalues

As has already been mentioned, in classical mechanics angular momentum 𝐿 is given

by 𝐿 = 𝑟⃗ × 𝑝⃗. But in quantum mechanics, L, r and p are operators which have the
Cartesian coordinates as show below

𝐿 = (𝐿𝑥 , 𝐿𝑦 , 𝐿𝑥 )

𝑃 = (𝑝𝑥 , 𝑝𝑦 , 𝑝𝑧 )

𝑟 = (𝑥, 𝑦, 𝑧)
Thus

39
 𝜕 𝜕
𝐿𝑥 = 𝑦𝑝𝑧 − 𝑧𝑝𝑦 = −𝑖ћ(𝑦 −𝑧 )
𝜕𝑧 𝜕𝑦
𝜕 𝜕
𝐿𝑦 = 𝑧𝑝𝑥 − 𝑥𝑝𝑧 = −𝑖ћ(𝑧 −𝑥 )
𝜕𝑥 𝜕𝑧
𝜕 𝜕
𝐿𝑧 = 𝑥𝑝𝑦 − 𝑦𝑝𝑥 = −𝑖ћ(𝑥 −𝑦 )
𝜕𝑦 𝜕𝑥
Also

𝐿2 = 𝐿𝑥 2 + 𝐿𝑦 2 + 𝐿𝑧 2

In the Cartesian coordinates, the commutation relations between 𝐿𝑗 (𝑗 = 𝑥, 𝑦, 𝑧) are

[𝐿𝑥 , 𝐿𝑦 ] = 𝑖ћ𝐿𝑧

[𝐿𝑦 , 𝐿𝑧 ] = 𝑖ћ𝐿𝑥

[𝐿𝑧 , 𝐿𝑥 ] = 𝑖ћ𝐿𝑦

It can be shown that

[𝐿2 , 𝐿𝑗 ] = 0

Which implies that

[𝐿2 , 𝐿𝑥 ] = [𝐿2 , 𝐿𝑦 ] = [𝐿2 , 𝐿𝑧 ] = 0

Lowering and Raising Operators

The raising operator is defined as

𝐿+ = 𝐿𝑥 + 𝑖𝐿𝑦

40
The lowering operator

𝐿− = 𝐿𝑥 − 𝑖𝐿𝑦
𝐿+ + 𝐿− 𝐿+ − 𝐿−
∴ 𝐿𝑥 = 𝑎𝑛𝑑 𝐿𝑦 =
2 2
𝐿+ and 𝐿− are not Hermitian.

Show that

[𝐿2 , 𝐿± ] = 0

[𝐿𝑧 , 𝐿± ] = ±𝐿±

[𝐿+ , 𝐿− ] = 2ћ𝐿𝑧

ALGEBRA OF ANGULAR MOMENTUM

The operators 𝐿2 𝑎𝑛𝑑 𝐿𝑧 describe physical quantities hence they must be Hermitian
operators, that is

(𝐿𝑧 )† = 𝐿𝑧 ⟹ (𝐿2 )† = 𝐿2
We now find the simultaneous eigen functions of both 𝐿2 and 𝐿𝑧 (|𝑙𝑚 >) which
comprise a complete orthogonal basis:

𝐿2 |𝑙𝑚 >= 𝑙(𝑙 + 1)ћ2 |𝑙𝑚 >

𝐿𝑧 |𝑙𝑚 >= 𝑚ћ|𝑙𝑚 >
When the lowering and raising operators act on |𝑙𝑚 >, they give the following

𝐿+ |𝑙𝑚 >= √𝑙(𝑙 + 1) − 𝑚(𝑚 + 1)ћ| 𝑙, 𝑚 + 1 >

41
 = √(𝑙 − 𝑚)(𝑙 + 𝑚 + 1)ћ|𝑙, 𝑚 + 1 >

𝐿− |𝑙𝑚 >= √𝑙(𝑙 + 1) − 𝑚(𝑚 − 1)ћ| 𝑙, 𝑚 − 1 >

= √(𝑙 + 𝑚)(𝑙 − 𝑚 + 1)ћ|𝑙, 𝑚 − 1 >

|𝑙𝑚 > is an eigenvector of 𝐿2 with eigenvalue 𝑙(𝑙 + 1)

Differential Representations

The representation of eigenvectors and eigenvalues is often more convenient using

spherical coordinates

𝑥 = 𝑟𝑠𝑖𝑛𝜃𝑐𝑜𝑠∅
𝑦 = 𝑟𝑠𝑖𝑛𝜃𝑠𝑖𝑛∅
𝑧 = 𝑟𝑐𝑜𝑠𝜃
The operators representing angular momentum in spherical coordinates are
𝜕 𝑐𝑜𝑠∅ 𝜕
𝐿𝑥 = 𝑖ћ(𝑠𝑖𝑛∅ + )
𝜕𝜃 𝑡𝑎𝑛𝜃 𝜕∅

𝜕 𝑠𝑖𝑛∅ 𝜕
𝐿𝑦 = 𝑖ћ(−𝑐𝑜𝑠∅ + )
𝜕𝜃 𝑡𝑎𝑛𝜃 𝜕∅
𝜕
𝐿𝑧 = −𝑖ћ
𝜕∅

2
𝜕2
2
1 𝜕 1 𝜕2
𝐿 = −ћ ( 2 + + )
𝜕𝜃 𝑡𝑎𝑛𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕∅2

42
 𝜕 𝜕
𝐿+ = ћ𝑒 𝑖∅ ( + 𝑖𝑐𝑜𝑡𝜃
𝜕𝜃 𝜕∅
𝜕 𝜕
𝐿− = ћ𝑒 −𝑖∅ (− + 𝑖𝑐𝑜𝑡𝜃
𝜕𝜃 𝜕∅
The eigenvectors of 𝐿2 and 𝐿𝑧 are functions that depend on angles 𝜃 𝑎𝑛𝑑 ∅ only
hence we can represent the wave function as

ѱ(𝑟, 𝜃, ∅) = 𝑅(𝑟)𝑌𝑙𝑚 (𝜃, ∅)

For a central potential 𝑉(𝑟) = 𝑉(𝑟). We find hat 𝑌𝑙𝑚 (𝜃, ∅) are spherical harmonics
where |𝑙𝑚 >= 𝑌𝑙𝑚 (𝜃, ∅)

Commutation Relation (Continued)

[𝐽𝑥 , 𝐽𝑦 ] = iћJZ [ J 2 , Jx ] = 0

[𝐽𝑦 , 𝐽𝑧 ] = 𝑖ћ𝐽𝑥 [𝐽𝑍 , 𝐽+ ] = ћ𝐽+

[𝐽𝑧 , 𝐽𝑥 ] = iћJy [Jz , J− ] = −ћJ−

[𝐽+ , 𝐽− ] = 2ћ𝐽𝑍 [𝐽𝑍 , 𝐽± ] = ±ћ𝐽±

[𝐽𝑥 + 𝑖𝐽𝑦 , 𝐽𝑥 − 𝑖𝐽𝑦 ]

𝐽2 |𝑗,𝑚〉 = 𝑗(𝑗 + 1)ћ2 |𝑗,𝑚〉

𝐽𝑍 |𝑗,𝑚〉 = 𝑚ћ|𝑗,𝑚〉

𝐽+ |𝑗, 𝑚〉 = √(𝑗 − 𝑚)(𝑗 + 𝑚 + 1)ћ|𝑗, 𝑚 + 1〉

𝐽− |𝑗, 𝑚〉 = √(𝑗 + 𝑚)(𝑗 − 𝑚 + 1)ћ|𝑗, 𝑚 − 1〉

43
𝐿𝑍 |𝑙,𝑚〉 = 𝑚ћ|𝑙,𝑚〉
𝐿2 |𝑙,𝑚〉 = 𝑙(𝑙 + 1)ћ2 |𝑙,𝑚〉
Example

Show that [𝐽2 , 𝐽𝑍 ] = 0

[𝐽𝑥 2 + 𝐽𝑦 2 + 𝐽𝑧 2 , 𝐽𝑧 ]

[𝐽𝑥 𝐽𝑥 , 𝐽𝑧 ] + [𝐽𝑦 𝐽𝑦 , 𝐽𝑧 ] + [𝐽𝑧 2 , 𝐽𝑧 ]

𝐽𝑥 [𝐽𝑥 , 𝐽𝑧 ] + [𝐽𝑥 , 𝐽𝑧 ]𝐽𝑥

𝐽𝑥 (−𝑖ћ𝐽𝑦 ) + −𝑖ћ𝐽𝑦 𝐽𝑥

[𝐽𝑦 , 𝐽𝑦 , 𝐽𝑧 ]

𝐽𝑦 [𝐽𝑦 , 𝐽𝑧 ] + [𝐽𝑦 , 𝐽𝑧 ]𝐽𝑦

𝑖ћ𝐽𝑦 𝐽𝑥 + 𝑖ћ𝐽𝑥 𝐽𝑦 = 0

[𝐽+ , 𝐽− ]

44
 Spherical Harmonics

The spherical polar coordinates (r,𝜃, ∅) of point P.

𝑥 = 𝑟 sin 𝜃 cos ∅
𝑦 = 𝑟 sin 𝜃 sin ∅
𝑧 = 𝑟 cos 𝜃
We have considered wave functions in Cartesian coordinates x, y and z. It is more
useful to consider wave function in spherical polar coordinates r, 𝜃 and ∅.

A quantum state represented by a wave function ψ(r,𝜃, ∅), the dependence on

𝜃 𝑎𝑛𝑑 ∅ specifies an angular shape that determines the orbital angular momentum
properties of the state. All possible angular momentum properties can be described
using the simultaneous eigen functions are called spherical harmonics and denoted
by

𝑌𝑙,𝑚𝑙 (𝜃, ∅) and they satisfy eigen value equations.

𝑌𝑙.𝑚𝑙 = 𝑙(𝑙 + 1)ћ2 𝑌𝑙.𝑚𝑙 and 𝐿2 𝑌𝑙.𝑚𝑙 = 𝑚𝑙 ћ𝑌𝑙.𝑚𝑙

Where the quantum numbers 𝑙 and 𝑚𝑙 can take values of 𝑙 = 0,1,2, … and 𝑚𝑙 =
−𝑙 … , +𝑙
These eigen functions are orthogonal because they satisfy

∫ 𝑌𝑙𝑜𝑟
1 𝑚1 𝑌𝑒,𝑚𝑙 𝑑𝛺 = 0
𝑙

If 𝑙11 ≠ 𝑙 𝑎𝑛𝑑 𝑚11 = and they are usually normalized so that

45
 ∫|𝑌𝑙,𝑚𝑙|2 𝑑𝛺 = 1

𝑑𝛺 is the solid angle

𝑑𝛺 = sin 𝜃 𝑑𝜃𝑑∅

The orbital angular momentum L and the orbital magnetic dipole moment µ𝐿 of an
electron –e moving in a Bohr orbit. The magnetic field β produced by the circulating
charge is indicated by the curved lines. The fictitious magnetic dipole that would
produce an identical field from the loop is indicated by its poles N, S.
−𝑧𝑒 2
𝑉 (𝑥, 𝑦, 𝑧) =
4𝜋𝜀0 √𝑥 2 +𝑦 2 +𝑧 2

If we express them in spherical coordinate the difficulty is removed.

−𝑧𝑒 2
𝑉 = 𝑉 (𝑟) = …………………… (1)
4𝜋𝜀0 𝑟

We express the TISE

−ћ2
⃗⃗ 2 µ(𝑟, 𝜃, 𝜓) + 𝑉 (𝑟)𝜓(𝑟, 𝜃, 𝜓) = 𝐸𝜓(𝑟, 𝜃, 𝜓) ………………………… (2)
𝑉
2µ

And the application operator is given by;

1 𝜕 𝜕 1 𝜕2 1 𝜕 𝜕
⃗⃗ 2 =
𝑉 (𝑟 2 )+ + (𝑠𝑖𝑛𝜃 ) ……………………….(3)
𝑟2 𝜕𝑟 𝜕𝑟 𝑟 2 𝑠𝑖𝑛2 𝜃 𝜕𝜓2 𝑟 2 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃

46
We assume a solution to the TISE

𝜓(𝑟, 𝜃, 𝜓) = 𝑅 (𝑟)-(𝜃)∅(𝜓) …………………… (4)

There are three solutions 𝜓(𝑟, 𝜃, 𝜓) to the equation (2) that split into parts of the
functions

R(r), (𝜃) and ∅(𝜓)

We substitute equation (4) and (3) into (2)

−ћ2 1 𝜕 𝜕𝑅−∅ 1 𝜕2 𝑅−∅ 1 𝜕 𝑠𝑖𝑛𝜃𝜕𝑅−∅
[ (𝑟 2 )+ + ( ) + 𝑉(𝑟)𝑅 − ∅ = 𝐸𝑅 − ∅]
2µ 𝑟2 𝜕𝑟 𝜕𝑟 𝑟 2 𝑠𝑖𝑛2 𝜃 𝜕𝜓2 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃

When we carry out particle partial differentiation

−ћ2 −∅ 𝜕 𝜕𝑅−∅ 𝑅𝐻 𝑑2 ∅ 𝑅∅ 𝑑 𝑑𝐻
[ (𝑟 2 )+ 2 + (𝑠𝑖𝑛𝜃 ) + 𝑉(𝑟)𝑅𝐻∅ = 𝐸𝑅𝐻∅]
2µ 𝑟 2 𝜕𝑟 𝜕𝑟 𝑟 2 𝑠𝑖𝑛2 𝜃 𝑑𝜑 𝑟 2 𝑠𝑖𝑛𝜃 𝑑𝜃 𝑑𝜃

2µ𝑟 2 𝑠𝑖𝑛2 𝜃
Multiplying through by -
𝑅𝐻∅ћ2

1 𝑑2 ∅ −𝑠𝑖𝑛2 𝜃 𝑑 2 𝑑𝑅 𝑠𝑖𝑛𝜃 𝑑 𝑑𝐻 2µ 2 2
= (𝑟 ) − (𝑠𝑖𝑛𝜃 ) − 𝑟 𝑠𝑖𝑛 𝜃 [𝐸 − 𝑉(𝑟)]
∅ 𝑑𝜑2 𝑅 𝑑𝑟 𝑑𝑟 𝐻 𝑑𝜃 𝑑𝜃 ћ2
The left side of the equation does not depend on the on R and 𝜃 and the right hand
side does not also depend on 𝜑 and their common value does not depend on any
variable and therefore must be a constant.
𝑑2 ∅
∴ = −𝑚𝑙 2 ∅ ……………………….. (5)
𝑑𝜑2

And

1 𝑑 2 𝑑 1 𝑑 𝑑𝐻 2µ𝑟 2 𝑚𝑙 2
− (𝑟 )− (𝑠𝑖𝑛𝜃 )− [𝐸 − 𝑉 (𝑟)] = −
𝑅 𝑑𝑟 𝑑𝑟 𝐻𝑠𝑖𝑛𝜃 𝑑𝜃 𝑑𝜃 ћ 𝑠𝑖𝑛2 𝜃

47
 1 𝑑 2 𝑑 2µ𝑟 2 𝑚𝑙 2 1 𝑑 𝑑𝐻
(𝑟 )+ [𝐸 − 𝑉(𝑟)] = − − (𝑠𝑖𝑛𝜃 )
𝑅 𝑑𝑟 𝑑𝑟 ћ 𝑠𝑖𝑛2 𝜃 𝐻𝑠𝑖𝑛𝜃 𝑑𝜃 𝑑𝜃
Left does not depend on the right side variables therefore both must be equal to
𝑙(𝑙 + 1)
1 𝑑 𝑑𝐻 𝑚𝑙 2 𝐻
− (𝑠𝑖𝑛𝜃 )+ = 𝑙(𝑙 + 1)𝐻 ………………………….. (6)
𝑠𝑖𝑛𝜃 𝑑𝜃 𝑑𝜃 𝑠𝑖𝑛2 𝜃

1 𝑑 𝑑𝑅 2µ 𝑅
(𝑟 2 )+ [𝐸 − 𝑉 (𝑟)]𝑅 = 𝑙(𝑙 + 1) ……………………… (7)
𝑟 2 𝑑𝑟 𝑑𝑟 ћ 𝑟2

Solution of equation (5) is given by;

∅(𝜓) = 𝑒 𝑖𝑚𝑙𝜓 and ψ=0 and ψ=2𝜋

∴ ∅(0) = ∅(2𝜋)

𝑒 𝑖𝑚𝑙0 = 𝑒 𝑖𝑚𝑙2𝜋
1=Cos𝑚𝑙 2𝜋 + 𝑖𝑆𝑖𝑛𝑚𝑙 2𝜋
|𝑚𝑙 | = 0,1,2,3 … +ve or –ve integer

∅𝑚𝑙 (𝜓) = 𝑒 𝑖𝑚𝑙𝜓

In solving for the function H(𝜃) we obtain acceptable solutions only if 𝑙 is equal to one
of the integers

𝑙 = |𝑚𝑙 |, |𝑚𝑙 | + 1, |𝑚𝑙 | + 2, |𝑚𝑙 | + 3 …

The acceptable solutions can be written as

−𝑙𝑚 (𝜃 ) = sin|𝑚𝑙 |𝜃𝐹𝑙|𝑚𝑙| (cos 𝜃 )

𝑙

And 𝐹𝑙|𝑚𝑙| (cos 𝜃 ) are polynomials in cos𝜃 that depends on the quantum number 𝑙
and |𝑚𝐿 |
48
 𝐹𝑙 𝑚𝑙 (cos 𝜃 ) = 𝑡ℎ𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑙𝑒𝑔𝑒𝑛𝑑𝑟𝑒 𝑝𝑜𝑙𝑦𝑛𝑜𝑚𝑖𝑎𝑙𝑠
R(r) has also accepted solution only if the total energy E has one of the values of

−µ𝑍 2 𝑒 4 −13.6
𝐸𝑛 = = 𝑒𝑉
(4𝜋𝜀0 )2 2ћ2 𝑛2 𝑛2
N=quantum number n= 𝑙 + 1, 𝑙 + 2, 𝑙 + 3

The acceptable solution must be conveniently be written as

𝑧𝑟⁄ 𝑍𝑟 𝑍𝑟
𝑅𝑛𝑒(𝑟) = 𝑒 − 𝑛𝑎0 ( ) 𝐺𝑛𝑙 ( )
𝑎0 𝑎0
0
4𝜋𝜀0 ћ2
And 𝑎0 = ⏞
= 𝐵𝑜ℎ𝑟 𝑟𝑎𝑑𝑖𝑢𝑠 ≅ 0.51 𝐴
µ𝑒 2

EXAMPLES OF Rne(r)

𝑛 𝑙 𝑚𝑙 𝐸𝑖𝑔𝑒𝑛 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑠
3
1 0 0 𝑍 ⁄2 −𝑧𝑟⁄𝑎
1
𝜓100 = ( ) 𝑒 0
√𝜋 𝑎0
2 0 0 3
1 𝑍 ⁄2 𝑧𝑟 −𝑧𝑟
𝜓200 = ( ) (2 − ) 𝑒 ⁄𝑎0
4√2𝜋 𝑎0 𝑎0
2 1 0 3
𝑍 ⁄2 𝑧𝑟 −𝑧𝑟⁄𝑎
1
𝜓210 = ( ) 𝑒 0 𝑐𝑜𝑠𝜃
𝑎
4√2𝜋 0 𝑎 0
2 1 ±1 3⁄
1 𝑍 2 𝑧𝑟 −𝑧𝑟⁄𝑎
𝜓21±1 = ( ) 𝑒 0 𝑠𝑖𝑛𝜃𝑒 ±𝑣𝑒
8√𝜋 𝑎0 𝑎0

n specifies the total energy of the atom hence the name principal quantum number.
Azimuthal Quantum number or orbital angular momentum depends
𝑙 is also called azimuthal quantum number.
49
𝑚𝑙 Because of the split in energy level it is called magnetic qu..

There are also situations with completely different eigen functions corresponding to
exactly the same total eigen value En. As the eigen function describes the behviour of
the atom which have states with completely different behavior but however, the
same total energy. This phenomenon is called degeneracy.

IDENTICAL PARTICLES

In classical mechanics, we can keep track of two particles 1 and 2 anywhere these
particles go. We can even colour as blue and red. We can examine how the red
particle moves as time passes.

In QM however, identical particles are truly indistinguishable. Because we can not

specify them by colour ie red and blue. We cannot also trace their trajectory because
that requires the position measurement at an instant of time (uncertainty principle).
The time independent Schrödinger equation of our system of two non-interacting
particles in three dimensions can be written as;
−ћ2 𝜕2 𝜓𝑇 𝜕2 𝜓𝑇 𝜕2 𝜓𝑇 ћ2 𝜕2 𝜓𝑇 𝜕2 𝜓𝑇 𝜕2 𝜓𝑇
( + + )− ( + + ) + 𝑉𝑇 𝜓 𝑇 = 𝐸𝑇 𝜓 𝑇 ……….. (1)
2𝑚 𝜕𝑥1 2 𝜕𝑦1 2 𝜕𝑧1 2 2𝑚 𝜕𝑥2 2 𝜕𝑦2 2 𝜕𝑧2 2

𝑚 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑖𝑡ℎ𝑒𝑟 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒

𝑥1 , 𝑦1 , 𝑧1 = 𝑡ℎ𝑒 𝑐𝑜𝑜𝑟𝑑𝑖𝑛𝑎𝑡𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 1
50
𝑥2 , 𝑦2 , 𝑧2 = 𝑡ℎ𝑒 𝑐𝑜𝑜𝑟𝑑𝑖𝑛𝑎𝑡𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 2
𝜓 𝑇 (𝑥1 … 𝑧2 ) = 𝑡ℎ𝑒 𝑒𝑖𝑔𝑒𝑛𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚
𝑉𝑇 (𝑥1 … 𝑧2 ) = 𝑡ℎ𝑒 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚
ET= the total energy for the total system since there is no interaction between the
two particles, they are more independent.

VT(𝑥1 … 𝑧2 ) = 𝑉(𝑥1 , 𝑦1 , 𝑧1 ) + 𝑉 (𝑥2 , 𝑦2 , 𝑧2 )

The total eigenfunction can be written as;

𝜓 𝑇 (𝑥1 … 𝑧2 ) = 𝜓(𝑥1 , 𝑦1 , 𝑧1 )𝜓(𝑥2 , 𝑦2 , 𝑧2 )

Where 𝜓(𝑥1 , 𝑦1 , 𝑧1 ) and 𝜓(𝑥2 , 𝑦2 , 𝑧2 ) satisfy identical one-particle time independent
Schrödinger equations..

We have the quantum numbers specifying the three space coordinates. There is also
one or more quantum numbers to specify the orientation of the spin of the particle.
We use α, β and to specify quantum numbers ie space and spin of a particle.

𝜓α (𝑥1 , 𝑦1 , 𝑧1 ) = 𝜓α (1)
𝜓β (𝑥2 , 𝑦2 , 𝑧2 ) = 𝜓β (2)

Eigen function of particle 1 in state α and 2 in state β

Total eigen function

𝜓 𝑇 (𝑥1 … 𝑧2 ) = 𝜓α (1)𝜓β (2) …………….. (2)

Total equation eigen function to specify particle 1 in state β and 2 in state α.

𝜓 𝑇 (𝑥1 … 𝑧2 ) = 𝜓β (1)𝜓α (2) ………………… (3)

We consider measurable quantity, the probability density

51
For equation (2)

𝜓 𝑇 ∗ 𝜓 𝑇 = 𝜓𝛼 ∗ (1)𝜓𝛽 ∗ (2)𝜓𝛼 (1)𝜓𝛽 (2) ……………………… (4)

And for equation (3) we have

𝜓 𝑇 ∗ 𝜓 𝑇 = 𝜓𝛽 ∗ (1)𝜓𝛼 ∗ (2)𝜓𝛽 (1)𝜓𝛼 (2) ……………………….. (5)

The particles are identical and indistinguishable so we should be able to exchange

their labeling without changing a measurable quantity such as probability density.

𝜓 𝑇 ∗ 𝜓 𝑇 = 𝜓𝛼 ∗ (1)𝜓𝛽 ∗ (2)𝜓𝛼 (1)𝜓𝛽 (2) →→ 𝜓 𝑇 ∗ 𝜓 𝑇 = 𝜓𝛼 ∗ (2)𝜓𝛽 ∗ (1)𝜓𝛼 (2)𝜓𝛽 (1)

1→ 2 2→ 1

Left changes to right, 1 changes to 2, 2 changes to 1.

The relabeled probability density function is not equal to the original function. It
must be emphasized that these are not acceptable eigenfunctions for the accurate
description of a system of identical particles.

Eigenfunctions which satisfy the TISE

1
𝜓𝑠 = [𝜓𝛼 (1)𝜓𝛽 (2) + 𝜓𝛼 (2)𝜓𝛽 (1)] …………………….. (5)
√2
1
𝜓𝐴 = [𝜓𝛼 (1)𝜓𝛽 (2) − 𝜓𝛼 (2)𝜓𝛽 (1)] ……………………… (6)
√2

Equation (5) Symmetric total eigenfunction

(6) antisymmetric total eigenfunction

52
Thus the total energy of the system containing a particle in quantum state α and
another in quantum state β will not depend on which particle is in which state if the
particles are identical.

Therefore both 𝜓 𝑇 = 𝜓𝛼 (1)𝜓𝛽 (2) and 𝜓 𝑇 = 𝜓𝛼 (1)𝜓𝛽 (2) are solutions to TISE
equation (1). Corresponding to the same value of the total energy E T. Because the
equation is linear in 𝜓 𝑇 , it follows immediately that the linear combinations 𝜓𝑆 𝑎𝑛𝑑 𝜓𝐴
of the two forms of 𝜓 𝑇 are also solutions. They correspond to the same value of ET,
therefore they are degenerate solutions that is 𝜓𝑆 𝑎𝑛𝑑 𝜓𝐴 are different eigenfunctions
corresponding to precisely the same eigen value. The phenomenon is called exchange
degeneracy since the difference between the degenerate eigen functions has to do
with exchange of the particle labels.

We now set out to show that the probability density function is unchanged. By
changing the particles label we have;
1
𝜓𝑠 = [𝜓𝛼 (1)𝜓𝛽 (2) + 𝜓𝛽 (1)𝜓𝛼 (2)] →→→
√2
1
[𝜓𝛼 (2)𝜓𝛽 (1) + 𝜓𝛽 (2)𝜓𝛼 (1)] = 𝜓𝑠 ……………………… (7)
√2
1
𝜓𝐴 = [𝜓𝛼 (1)𝜓𝛽 (2) − 𝜓𝛽 (1)𝜓𝛼 (2)] →→→
√2
1
[𝜓𝛼 (2)𝜓𝛽 (1) − 𝜓𝛽 (2)𝜓𝛼 (1)] = −𝜓𝐴 ………………… (8)
√2
From the above equation (7) and (8) we see that the symmetric total
equation function 𝜓𝑆 is unchanged by the exchange of particles labels and
that the antisymmetric total eigen function 𝜓𝐴 is a multiplied by minus (-)
by an exchange the particle labels. The properties give rise to their names.
We now show the probability densities;
𝜓𝑆 ∗ 𝜓𝑆 →→ 𝜓𝑆 ∗ 𝜓𝑆
𝜓𝐴 ∗ 𝜓𝐴 →→ (−1)2 𝜓𝐴 ∗ 𝜓𝐴 = 𝜓𝐴 ∗ 𝜓𝐴

53
 Electron, protons, neutrons have spin 𝑠 = 1⁄2, the deuterium nucleus 2
𝐻 has spin=1 and Helium
4
nucleus 𝐻𝑒 has spin s=0 hence for both symmetric and antisymmetric total eigenfunctions, the
probability density functions are not changed by the exchange of the particle labels.
We can also use determinants to find the antisymmetric and symmetric eigen functions
Eg.
1
𝜓𝐴 = [𝜓𝛼 (1)𝜓𝛽 (2) − 𝜓𝛼 (1)𝜓𝛽 (2)]
√2
Slater determinants can be used as follows;
1 𝜓𝛼 (1) 𝜓𝛼 (2)
𝜓𝐴 = | |
√2 𝜓𝛽 (1) 𝜓𝛽 (2)

Where 2!= 2x1=2

For three particles we have
𝜓𝛼 (1) 𝜓𝛼 (2) 𝜓𝛼 (3)
1
𝜓𝐴 = | 𝜓𝛽 (1) 𝜓𝛽 (2) 𝜓𝛽 (3) |
√3! 𝜓 (1) 𝜓 (2) 𝜓 (3)
𝛾 𝛾 𝛾
Where 3!= 3x2x1 = 6
When we expand the determinant is given by;
1
𝜓𝐴 = [𝜓𝛼 (1)𝜓𝛽 (2)𝜓𝛾 (3) + 𝜓𝛽 (1)𝜓𝛾 (2)𝜓𝛼 (3) + 𝜓𝛾 (1)𝜓𝛼 (2)𝜓𝛽 (3) − 𝜓𝛾 (1)𝜓𝛽 (2)𝜓𝛼 (3)
√3!
− 𝜓𝛽 (1)𝜓𝛼 (2)𝜓𝛾 (3) − 𝜓𝛼 (1)𝜓𝛾 (2)𝜓𝛽 (3)]

It can be written for symmetric wave function. We use the linear combination.

THE EXCLUSIVE PRINCIPLE.

In a multi-electron atom there can never be more than one electron in the same quantum state. The anti-symmetric
total eigenfunction which is given by;
1
𝜓𝐴 = [𝜓𝛼 (1)𝜓𝛼 (2) − 𝜓𝛼 (1)𝜓𝛼 (2)] ≡ 0
√2
When both particles are in the same space and spin quantum state.
Hence if two particles are described by the anti-symmetric total eigenfunction, they cannot both be a state with the
same space and spin quantum numbers. The Pauli exclusive principle plays a governing role in determining the
physical and chemical properties of atoms and leads us to an understanding of the periodic table of the elements. It
has a crucial role in determining the electrical and thermal properties of electrons in solids.

Bosons & Fermions

Bosons are particles with integer spin or zero spin and system of identical bosons must have quantum states that are
symmetric when the two particles are exchanged ie must have total symmetric eigenfunction.
54
Eg α-particle, 42𝐻𝑒 (spin=0), photon (spin=1), deuterium (spin =1), phonons (spin =0)
Fermions on the other hand are particles with half-integer spin and systems of identical fermions must have quantum
states which are anti-symmetric (ie total anti-symmetric eigenfunctions) when two particles are exchanged.
Because electrons are spin half particles, they are indistinguishable in the fermion way. They never have symmetric
1 1
states but only antisymmetric states eg. Protons, neutrons, electrons, 3𝐻 (𝑠𝑝𝑖𝑛 = 2), 1𝐻 (𝑠𝑝𝑖𝑛 = 2)
The bosom way of being indistinguishable also leads to important phenomena. Because bosons are described by
symmetric quantum states, many bosons may occupy the same single-particle state and when this happens quantum-
mechanical behavior of macroscopic scale arises. The most important example of bosons togetherness is the
coherence arise because photons are bosons with spin one, have probabilities to have the same energy and
momentum in which the same way as two particles with symmetric wave function have a high probability of being
at the same location. Bosom togetherness is also responsible for the superfluidity of liquid helium consisting of
weakly interacting helium at temperature below 2.2 K. Liquid helium consists of weakly interacting helium atoms
which behave like bosons because they consists of 4He nucleus spin zero and two electrons with a combine spin of
zero. At low temperatures a considerable fraction of atoms in liquid helium ‘condense’ into the lowest energy state.
They form Bose-Einstein condensate which are coherent with each other and move collectively without friction.
Recently almost pure Bose-Einstein condensate have been produced by cooling atoms in magnetic traps; indeed the
2001 Noble Prize in physics awarded Eric Cornell, Wolfgang Ketterle and Carl Wiemann for their work in producing
the first pure Bose-Einstein condensates in 1995.
Surprisingly, boson-like togetherness also occurs in situations where fermion-like behavior is expected. It occurs in
the superconductivity of metals at low temperatures because pairs of electrons act like indistinguishable bosons. It
occurs in the superconductivity of metals at low temperatures because pairs of electrons act like indistinguishable
bosons. It also probably occurs when liquid helium-3 becomes a superfluid at very low temperatures. Helium-3
atoms become a superfluid at very low temperatures. Helium -3 atoms, unlike the normal helium atoms are fermions
because 3He has spin half, but pairs of helium-3 atoms can act like a system of indistinguishable bosons and give
arise to collective motion with no friction in liquid helium-3.

55
 Helium II will "creep"
along surfaces in order to
find its own level—after a
short while, the levels in
the two containers will
equalize

Quantum statistics

56
Bosons obey Bose-Einstein statistics and the probability of occupation f(E) of energy
levels (E) at absolute temperature is given by;
1
𝑓(𝐸 ) = (𝐸−𝜇)/𝑘𝑇
𝑒 −1
Where 𝜇 = 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙
K= Boltzmann constant
Fermions on the other hand obey Fermi-Dirac statistics and the probability of
occupation an energy level given by;
1
𝑓(𝐸 ) = (𝐸−𝜇)/𝑘𝑇
𝑒 +1
For an electron if 𝜇 = 𝐸𝐹 = 𝐹𝑒𝑟𝑚𝑖 𝑒𝑛𝑒𝑟𝑔𝑦 = 𝐹𝑒𝑟𝑚𝑖 𝑙𝑒𝑣𝑒𝑙
1
∴ 𝑓(𝐸 ) =
𝑒 (𝐸−𝐸𝑓)/𝑘𝑇 + 1

We now sketch various graphs when T increases

At increases, more and more of the electrons are excited to states with𝐸 > 𝐸𝑓 .

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At absolute zero, all the states are occupied (occupation probability) at energy up to
EF0. f(E)
At absolute zero, all the
states occupied up to Ef0

Ef0 (all the states after Ef0 are empty and the probability of
occupation equals zero)

Starke Effect

Starke effect is the splitting of the energy levels of the hydrogen atom (or
other/atoms) resulting from the application of an electric field. If an electric field is
applied, its effect is viewed as perturbation and is evaluated within the framework of
time-independent perturbation theory for degenerate levels,

TIME INDEPENDENCE PERTURBATION THEORY

We assume a Hamilton H0 which is time independent and has known energy levels
arising from TISE.

𝐻0 |𝑛(0) 〉 = 𝐸𝑛 (0) |𝑛(0) 〉 ………………………………… (1) But 𝑛 = 1,2,3, …

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Superscript (0) shows that the quantities are associated with the unperturbed
system. We now introduce a perturbation V which is a Hamiltonian of a weak physical
disturbance like external electric field V is Hermitian. We also introduce
dimensionless parameter 𝜆 ranging from 0 (no perturbation) to 1(full perturbation).

The perturbed Hamiltonian are given by

𝐻 = 𝐻0 + 𝜆𝑉………………….. (3)

The energy levels and eigenstates of the perturbed Hamiltonian are given by;
(𝐻0 + 𝜆𝑉)|𝑛〉 = 𝐸𝑛 |𝑛〉 ………………… (4)

If the perturbation is sufficiently weak, we can write En and |𝑛〉 as a power series.

𝐸𝑛 = 𝐸𝑛 (0) + 𝜆𝐸𝑛 (1) + 𝜆2 𝐸𝑛 (2) +…. ……………………. (5)

|𝑛〉 = |𝑛(0) 〉 + 𝜆|𝑛(1) 〉 + 𝜆2 |𝑛2 〉 + … ……………………. (6)

Substituting (5) and (6) into (4) we have;

(𝐻0 + 𝜆𝑉)(|𝑛(0) 〉 + 𝜆|𝑛(1) 〉 + ⋯ ) = (𝐸𝑛 (0) + 𝜆𝐸𝑛 (1) + 𝜆2 𝐸𝑛 2 + ⋯ )(|𝑛(0) 〉 +

𝜆|𝑛(1) 〉 + ⋯ )

Expanding and putting λ=1

The first order equation is given by;

𝐻0 |𝑛(1) 〉 + 𝑉|𝑛(0) 〉 = 𝐸𝑛 (0) |𝑛(1) 〉 + 𝐸𝑛 (1) |𝑛(0) 〉 …………………….. (7)

From the above equation we can say that

𝐻0 |𝑛(1) 〉 = 𝐸𝑛 (0) |𝑛(1) 〉 or

𝐸𝑛 (1) |𝑛(0) 〉= 𝑉|𝑛(0) 〉

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Multiplying through by 〈𝑛(0) | 〈𝑛(0) |𝑛(1) 〉 = 0 , 〈𝑛(0) |𝑛(0) 〉 = 1

𝐸𝑛 (1) = 〈𝑛(0) |𝑉|𝑛(0) 〉 ……………………………………… (8)

We use the resolution identity

𝑉|𝑛(0) 〉 = (∑𝑘≠𝑛|𝑘 (0) 〉〈𝑘 (0) |)𝑉|𝑛(0) 〉 + (|𝑛(0) 〉〈𝑛(0) |)𝑉|𝑛(0) 〉

= ∑𝑘≠𝑛|𝑘 (0) 〉〈𝑘 (0) |𝑉|𝑛(0) 〉 + 𝐸𝑛 (1) |𝑛(0) 〉 …………………… (9)

𝑆𝑖𝑛𝑐𝑒 𝐸𝑛 (1) = 〈𝑛(0) |𝑉|𝑛(0) 〉

Where |𝑘 (0) 〉 is the orthogonal complement of the |𝑛(0) 〉 and from equations (7) and
(9) we have;

(𝐸𝑛 (0) − 𝐻0 )|𝑛(1) 〉 = ∑ |𝑘 (0) 〉〈𝑘 (0) |𝑉|𝑛(0) 〉

𝑘≠0

Suppose the zeroth-order energy level is not degenerate and we multiply through by
<𝑘 (0) 〉 we have;

(𝐸𝑛 (0) − 𝐻0 )〈𝑘 (0) |𝑛(1) 〉 = 〈𝑘 (0) |𝑉|𝑛(0) 〉

(1) 〉
〈𝑘 (0) |𝑉|𝑛(0) 〉
|𝑛 =∑ (0) (0)
|𝑘 (0) 〉
𝑘≠𝑛
𝐸𝑛 − 𝐸𝑘

|𝑛(1) 〉 is proportional to 〈𝑘 (0) |𝑉|𝑛(0) 〉 and inversely proportional to the energy

difference between eigen states k and n. Therefore, the perturbation deforms the
eigen state to greater extent if there are more eigen states at nearby energies.

Second order

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 (0) 0 (0) 〉
|𝑘 (0) |𝑉|𝑛(0) |2
𝐸𝑛 = 𝐸𝑛 + 〈𝑛 |𝑉|𝑛 +∑ (0) (0)
𝑘≠𝑛
𝐸𝑛 − 𝐸𝑘

(0) 〉
|𝑘 (0) 〉〈𝑘 (0) |𝑉|𝑛(0) 〉 (0) 〉
〈𝑘 (0) |𝑉|𝑙(0) 〉〈𝑙(0) |𝑉|𝑛(0)
|𝑛〉 = |𝑛 +∑ (0) (0)
+ ∑ ∑ |𝑘
𝐸𝑛 − 𝐸𝑘 𝑘≠𝑛 𝑙≠𝑛
(𝐸𝑛 (0) − 𝐸𝑘 (0) )(𝐸𝑛 (0) − 𝐸𝑙 (0) )

Tutorials

a) What is the lowest possible energy ( in eV) of an electron in hydrogen if its

orbital angular momentum is √12ћ
b) What are the largest and smallest values of the Z-component of the orbital
angular momentum (in terms of ћ) for the electron in part (a)?
c) What are the smallest largest values of the spin angular momentum (in terms of
ћ) for the electron in part (a)?
d) What are the smallest largest values of the orbital angular momentum (in terms
of ћ) for an electron in the M shell of hydrogen?
Consider an electron in hydrogen having total energy of 0.5440 eV.
a) what are the possible values of its orbital angular momentum (in terms of
ћ)?
b) What wavelength of light would it take to excite this electron to the next
higher shell? Is this photon visible to humans?

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c) 𝑓(𝑥 ) = ∑𝛼𝑛=0 𝑎𝑛 (𝑥 − 𝑐)𝑛 = 𝑎0 + 𝑎1 (𝑥 − 𝑐)1 + 𝑎2 (𝑥 − 𝑐)2 +
𝑎3 (𝑥 − 𝑐)3 . ..
d) When C=0
e) 𝑓(𝑥 ) = ∑𝛼𝑛=0 𝑎𝑛 𝑥 𝑛 = 𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + 𝑎3 𝑥 3 . ..
f) [J2,Jx]=0 𝐽2 |𝑗, 𝑚〉 = 𝑗(𝑗 + 1)ћ2 |𝑗,𝑚〉
g) 𝐽+ |𝑗, 𝑚〉 = ћ√𝑗(𝑗 + 1) − 𝑚(𝑚 + 1)|𝑗,𝑚 + 1〉
h)
i) 𝐽− |𝑗, 𝑚〉 = ћ√𝑗(𝑗 + 1) − 𝑚(𝑚 + 1)|𝑗,𝑚 − 1〉

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