Quantum Mechanic II Lectures Note
Uploaded by
Bereket YohanisQuantum Mechanic II Lectures Note
Uploaded by
Bereket YohanisMizan Tepi University
College of Natural and Computational College
Department of Physics
Quantum Mechanics II (phy2073)
Lectures note
By Takele Kekeba Emana
E-mail address: [email protected]
Phone number: +251911788480
Mizan-Tepi University
June, 2020
Tepi, Ethiopia
Table of Contents
CHAPTER ONE----------------------------------------------------------------------------------------------- 1
1. ANGULAR MOMENTUM ------------------------------------------------------------------------------ 1
1.1. Angular Momentum Operator ----------------------------------------------------------------------- 1
1.2. Representation of angular momentum in spherical co-ordinate -------------------------------- 2
1.3. Square of angular momentum operator ----------------------------------------------------------- 13
1.4. Commutation rules ----------------------------------------------------------------------------------- 21
1.4.1. Position- Angular momentum operator commutation relation --------------------------- 22
1.4.2. Momentum angular momentum operator commutation relation ------------------------- 23
1.4.3. Angular momentum - angular momentum commutation relation ------------------------ 24
1.5. Eigen value of 𝐿𝑧 and 𝐿2 --------------------------------------------------------------------------- 29
1.6. Eigen function of angular momentum operator -------------------------------------------------- 46
1.7. Matrix representation of angular momentum operator------------------------------------------ 57
1.8. Spin, spin operator, pauli’s spin matrices --------------------------------------------------------- 67
CHAPTER TWO --------------------------------------------------------------------------------------------- 83
2. THE HYDROGEN ATOM ------------------------------------------------------------------------------ 83
2.1. Reduction to one body problems ------------------------------------------------------------------- 85
2.2. Separation of Variables (Separation of the Center of Mass Motion), Spherical eigen
function ----------------------------------------------------------------------------------------------------- 91
2.2.1. Solution of the Center of mass Equation for the Hydrogen Atom ----------------------- 93
2.3. Solution of the Radial Equation (relative motion) for the Hydrogen Atom ----------------- 95
2.3.1. The angular dependency of solution ---------------------------------------------------------- 96
2.3.2. Hydrogen Wave function (spherical and radial wave function) -------------------------- 96
2.3.3. Atomic energy level, quantum number ---------------------------------------------------- 106
2.4. Radial wave function 𝑅𝑛𝑙𝑟 of the hydrogen atom --------------------------------------------- 108
2.5. Radial wave function with Laguerre polynomials --------------------------------------------- 114
2.6. Associated Laguerre polynomial ----------------------------------------------------------------- 115
2.7. Eigen Values, Quantum Numbers and Degeneracy ------------------------------------------- 122
2.7.1. Degeneracy of Hydrogen atom -------------------------------------------------------------- 125
Chapter 3 ---------------------------------------------------------------------------------------------------- 130
3. Perturbation method ------------------------------------------------------------------------------------ 130
3.1. Types of perturbation Theory -------------------------------------------------------------------- 132
i
3.1.1. Time independent perturbation Theory (TIPT) ------------------------------------------- 132
3.1.2. Time –dependent perturbation Theory ----------------------------------------------------- 148
ii
CHAPTER ONE
1. ANGULAR MOMENTUM
⃗ is defined as the cross-product of position
Classically the angular momentum vector 𝐿
vector 𝑟 and the momentum vector 𝑝.
Lrp 1.1
In Cartesian component, Eq. (1.1) can be written as:
iˆ ˆj kˆ
Lrp x y z
p py pz
x
L ypz zp y iˆ zpx xpz ˆj xp y ypx kˆ 1.2
L Lxiˆ Ly ˆj Lz kˆ 1.3
⃗ is given as:
Therefore, the component of 𝐿
Lx ypz zp y 1.4
Ly zpx xpz 1.5
Lz xp y ypx 1.6
The square of the angular momentum is given by
L2 L L L2x L2y L2z 1.7
1.1. Angular Momentum Operator
In quantum mechanics, operators can be constructed by taking the corresponding
dynamical variable of classical mechanics which is expressed in terms of coordinates,
linear momentum and angular momentum and replacing:
The position vector 𝑟 by operator 𝑟̂ = (𝑥̂, 𝑦̂, 𝑧̂ ),
The momentum vector 𝑝 by the momentum vector operator 𝑝̂ = (𝑝̂𝑥 , 𝑝̂𝑦 , 𝑝̂𝑧 ) =
𝜕 𝜕 𝜕
(−𝑖ℏ 𝜕𝑥 , −𝑖ℏ 𝜕𝑦 , −𝑖ℏ 𝜕𝑧)
1
⃗ by angular momentum operator 𝐿̂ = (𝐿̂𝑥 , 𝐿̂𝑦 , 𝐿̂𝑧 )
The angular momentum vector 𝐿
The angular momentum operator 𝐿̂ is given by:
Lˆ rˆ pˆ rˆ i 1.8
Since position coordinator operator and linear momentum operators are hermitian we can
apply the following relation:
xˆ x, pˆ x i
x
yˆ y, pˆ z i 1.9
y
yˆ y, pˆ z i
y
Therefore, the component of angular momentum operator 𝐿̂ is given by:
Lˆx yp
ˆ ˆ z zp
ˆˆ y
y i z i
z y
yi zi
z y
Lˆx i y z 1.10
z y
Lˆ y zp
ˆ ˆ x xp
ˆˆ z i z x 1.11
x z
Lz xpˆˆ y yp
ˆ ˆ x i x y 1.12
y x
1.2. Representation of angular momentum in spherical co-ordinate
Spherical rotational symmetry is inherent to angular momentum, it is convenient to express
angular momentum in terms of spherical coordinates.
Spherical coordinates are related to Cartesian coordinates (𝑥, 𝑦, 𝑧 ) through the
transformation.
2
Where
𝑟 − is radius (position)
𝜃 −is the polar angle and
𝜙 −is the azimuthal angle
Figure 1: spherical coordinate
From Fig. (1), we have
opp. side a x2 y 2
sin
hypo. side r r
a r sin 1.13
adj.side z
cos
hypo. r
z r cos 1.14
r x2 y 2 z 2 1.15
a x2 y 2
tan 1.16
z z
x2 y 2
tan 1
1.17
z
3
Again from Fig. (1):
adj.side x x
cos 1.18
hypo. a x2 y 2
x a cos , sin ce a r sin
x r sin cos 1.19
opp.side y x
sin
hypo. a x2 y 2
y a sin , but a r sin
y r sin sin 1.20
y
tan 1.21
x
y
tan 1 1.22
x
The relationship between spherical coordinate and Cartesian coordinate is given:
x r sin cos 1.23
y r sin sin 1.24
z r cos 1.25
𝜕
We know proceeds to calculate the angular momentum operators, the first step is to write 𝜕𝑥𝑖
in the spherical coordinates.
We use the chain rule and the above transformation from Cartesian to spherical ultimately all
of these should be written in the spherical coordinates.
4
r
1.26
x x r x x
r
1.27
y y r y y
r
1.28
z z r z z
Computing the partial derivatives, we start with the differential of 𝑟 interms of (𝑥, 𝑦, 𝑧)
r x2 y 2 z 2 x2 y 2 z 2
1
2
1 1 1
x y z 2 xdx x y z 2 ydy x y z 2 zdz
1 2 2 2 2 1 1 2 2 2 2 1 1 2 2 2 2 1
dr x, y , z
2 2 2
1 1 1
x2 y 2 z 2 xdx x 2 y 2 z 2 ydy x 2 y 2 z 2
2 2 2 zdz
1 1 1
xdx ydy zdz
x y z
2 2 2
x y z
2 2 2
x y2 z2
2
x y z
dr x, y , z dx dy dz 1.29
r r r
We take partial derivative of Eq.(1.29) with respect to (𝑥, 𝑦, 𝑧), we obtain the following
relation:
r x y z x
dx dy dz 1.30
x x r r r r
x y z y
dx dy dz 1.31
y y r r r r
x y z z
dx dy dz 1.32
z z r r r r
For 𝜃, we take differential of Eq. (1.16) in terms of (𝑥, 𝑦, 𝑧):
x2 y 2
tan
z
'
sin x y
' 2 2
cos x, y, z
z
sin cos sin cos
' ' '
1
1 1
cos 2
2
1 2
x y
2 2 1 2 xdx
z
2
1 2
x y
2 2 1 2 ydy
z
x2 y 2
z
5
cos cos d sin sin d 1 1
1 ' z ( z ) '
cos
2
x 2
y
2 2 xdx
x 2
y
2 2 ydy
x2 y 2
z2
z z
cos sin d
2 2
x y
1 1
dz
cos 2
2
2 2 xdx
z
x y
2 2 2 ydy
z
x2 y 2 2
z
d 1 x 1 y x2 y 2
dx dy dz
cos 2 x2 y 2 z x2 y 2 z z2
1 x 1 y x2 y 2
d cos 2 dx cos 2 dy 2
cos 2 dz 1.33
x y
2 2 z
x y
2 2 z z
From Eq. (1.14), we have
z r cos
z 2 r 2 cos 2
z2
cos 2
2
1.34
r
Substituting Eq. (1.33) in to Eq.(132), we obtain:
1 x z2 1 y z2 x2 y 2 z 2
d 2
dx 2
dy dz
x2 y 2 z r x2 y 2 z r z2 r2
1 xz 1 yz x2 y 2
d 2
dx 2
dy dz 1.35
x2 y 2 r x2 y 2 r r2
We take partial derivative of Eq. (1.35) with respect to (𝑥, 𝑦, 𝑧), we get the following result:
1 xz 1 yz x2 y 2 1
xz
dx dy dz 1.36
x x x 2 y 2 r 2 2
2 r2 r2 x y r
2 2 2
x y
1 xz 1 yz x2 y 2 1 yz
dx dy dz 1.37
y y x 2 y 2 r 2
x y
2 2 r 2
r 2
x y
2 2 r2
1 xz 1 yz x2 y 2 x2 y 2
dx dy dz
1.38
z z r2 2
r2 r2
x y x2 y 2 r
2 2
6
Finally, we compute the differential of 𝜙 from Eq.(1.21) with respect to (𝑥, 𝑦, 𝑧), we obtain:
y
tan
x
'
tan
' y
x
d xdy ydx x y
2 dy 2 dy
cos 2
x 2
x x
d 1 y
dy 2 dx
cos x
2
x
1 y
d cos 2 dy 2 cos 2 dx 1.39
x x
From Eq. (1.18), we have:
x x
cos
a x y2
2
2
x
cos 2 2
2
x y
x2
cos 2 2 1.40
x y2
Put Eq. (1.40) in to Eq. (1.39), we obtain:
1 x2 y x2
d dy dx
x x2 y 2 x2 x2 y 2
x y
d 2 dy 2 dx 1.41
x y 2
x y2
We take partial derivative of Eq. (1.41) with respect to (𝑥, 𝑦, 𝑧), we obtain:
x y y
2 dy 2 dx 2 1.42
x x x y 2
x y 2
x y
2
x y x
2 dy 2 dx 2 1.43
y y x y 2
x y 2
x y
2
x y
2 dy 2 dx 0 1.44
z z x y 2
x y 2
7
Now we returning to the chain rule expansion, we substitute Eq.(1.30), Eq. (1.36) and
𝜕
Eq.(1.42) in to Eq.(1.26), we obtain the result of 𝜕𝑥:
r r x xz y
, where , , 2
x x r x x x r x r 2 x 2 y 2 x x y2
x xz y
2 1.45
x r r r x y x y
2 2 2 2
Put Eq.(1.23), (1.24) and Eq.(1.25) into Eq. (1.45), we obtain:
r sin cos r sin cos r cos r sin sin
x r r r 2 r 2 sin 2 cos 2 r 2 sin 2 sin 2 r 2 sin 2 cos 2 r 2 sin 2 sin 2
r sin cos r 2 sin cos cos r sin sin
r r
r2 r 2 sin 2 cos 2 sin 2 r 2 sin 2 cos 2 sin 2
1 1
sin cos cos sin sin
sin cos
r r sin r sin 2
1 1 sin
sin cos cos cos 1.46
x r r r sin
Substituting Eq.(1.31), Eq. (1.37), Eq.(1.43) into Eq.(1.27), we obtain we obtain the
𝜕
result of 𝜕𝑦:
r r y yz x
, where , , 2
y y r y y y r y r x y y x y 2
2 2 2
y yz x
2
r r r x y x y
2 2 2 2
r sin sin
r sin sin r cos
r sin cos
r r r 2 r 2 sin 2 cos2 r 2 sin 2 sin 2 r 2 sin 2 cos2 r 2 sin 2 sin 2
r sin sin r 2 sin sin cos r sin cos
r r 2 2
r2 r sin cos sin
2 2 2 r 2
sin 2
cos sin 2
1 1
sin sin cos sin cos
sin sin
r r sin r sin 2
1 1 cos
sin sin cos sin 2.47
y r r r sin
8
Finally, we substitute Eq.(1.32), Eq.(1.38), and Eq.(1.44) into Eq.(1.28), we obtain the result
𝜕
of 𝜕𝑧:
r r Z x 2 y 2
, where , , 0
z z r z z z r z r2 z
Z x2 y 2
r r r2
r cos r 2 sin 2 cos 2 r 2 sin 2 sin 2
r r r2
r 2 sin 2 cos 2 s sin 2
cos
r r2
r sin
cos 2
r r
1
cos sin 1.48
z r r
When we substituting Eq.(1.46), Eq.(1.47) and Eq.(1.48) into Eq.(1.10), Eq.(1.11) and
Eq.(1.12), we obtain angular momentum operator 𝐿̂ in spherical coordinate.
Lˆx i y z
z y
1
r sin sin cos r r sin
i
1 1 cos
r cos sin sin cos sin
r r r sin
1
r sin sin cos r r sin sin r
sin
r cos sin sin
r
i
1 1 cos
r cos r cos sin r cos r sin
i sin 2 sin cos 2 sin cot cos
i sin sin 2 cos 2 cot cos
1
9
i sin cot cos
i sin cot cos
Lˆx i sin cot cos 1.49
Lˆ y i z x
x z
1 1 sin
r cos sin cos cos cos
r r r sin
i
1
r sin cos cos sin
r r
1 1 sin
r cos sin cos r r cos r cos cos r cos r sin
i
1
r sin cos cos r r sin cos r sin
i cos 2 os sin 2 cos cot sin
i cos cos 2 sin 2 cot sin
1
Lˆ y i cos cot sin 1.50
Lˆz i x y
y x
1 1 cos
r sin cos sin sin cos sin
r r r sin
i
1 1 sin
r sin sin sin cos cos cos
r r r sin
10
1 cos
r sin cos sin sin r sin cos cos sin r sin cos
r r r sin
i
1 sin
r sin sin sin cos r sin sin cos cos r sin sin
r r r sin
i cos 2 sin 2
i cos 2 sin 2
1
Lˆz i 1.51
Raising and lowering operators in terms of spherical coordinate
i. 𝐿̂+ = 𝐿̂𝑥 + 𝑖𝐿̂𝑦 raising operator (1.52)
Substituting Eq. (1.49) and Eq.(1.50), we obtain the raising (step-up) operator:
Lˆ Lˆx iLˆ y , Lˆx i sin cot cos and Lˆ y i cos cot sin
i sin cot cos i i cos cot sin
i sin cot cos i 2 cos cot sin , i 2 1
i sin cot cos cos cot sin
i sin i cot cos cos cot sin , rearrange like terms
cos i sin i cot cos cot sin
cos i sin i cos sin cot
, using by trick
11
= cos i sin i cos i sin cot because, i 2 1
= cos i sin i cos i sin cot , hence, cos i sin e i
ei ei
ei iei cot
Lˆ ei i cot 1.53
ii. 𝐿̂− = 𝐿̂𝑥 − 𝑖𝐿̂𝑦 lowering (step-down) operator (1.54)
Lˆ Lˆx iLˆ y , Lˆx i sin cot cos and Lˆ y i cos cot sin
i sin cot cos i i cos cot sin
i sin cot cos i 2 cos cot sin , i 2 1
i sin cot cos cos cot sin
i sin i cot cos cos cot sin , rearrange like terms
cos i sin i cot cos cot sin
cos i sin i cot cos cot sin
cos i sin i cos sin cot
cos i sin i cos i sin cot
12
= cos i sin i cos i sin cot , hence, cos i sin ei
e i e i
ei iei cot
Lˆ ei i cot 1.55
1.3. Square of angular momentum operator
The square of the angular momentum is given by
3
L2 L2x L2y L2z Li
i 1
Whereas the spherical coordinate representation of the square of the angular momentum
operator is:
3
Lˆ2 Lˆ2x Lˆ2y Lˆ2z Lˆ2i 1.56
i 1
Let us see each component of angular momentum operator in spherical coordinate system:
Lˆ2x Lˆx Lˆx
i sin cot cos i sin cot cos
i sin cot cos sin cot cos
2
sin cot cos sin cot cos
2
sin sin sin cot cos cot cos sin
Lˆ2x 2 1.57
I II III
cot cos cot cos
IV
13
Eq. (1.57) can be solved by application of product rule differentiation method.
2
I sin sin sin 2
1.58
2
II sin cot cos
sin cot cos sin cot cos
II sin csc2 cos sin cot cos 1.59
III cot cos sin
cot cos sin cot cos sin
cot cos cos cot cos sin
cot cos 2 cot cos sin 1.60
IV= cot cos cot cos
cot cos cot cos cot cos cot cos
2
cot 2 cos sin cot 2 cos 2 2 1.61
Substituting Eq.(1.58), Eq.(1.59), Eq.(1.60) and Eq.(1.61) into Eq.(1.57), we obtain:
2 2
sin 2 sin csc cos sin cot cos cot cos
2 2
Lˆ2x 2 1.62
2
cot cos sin cot cos sin cot cos 2
2 2 2
14
Lˆ2y Lˆ y Lˆ y 1.63
i cos cot sin i cos cot sin
(i )2 cos cot sin . cos cot sin
cos cos cos cot sin cot sin cos
Lˆ2y 2 1.64
A B C
cot sin cot sin
D
Applying the same procedures, Eq.(1.64), can be solved by application of product rule
differentiation method.
2
A cos cos cos 2
1.65
2
B cos cot sin
cos cot sin cos cot sin
cos csc2 sin cos cot sin 1.66
C cot sin cos
cot sin cos cot sin cos
cot sin 2 cot sin cos 1.67
15
D cot sin cot sin
cot sin cot sin cot sin cot sin
2
cot 2 sin cos cot 2 sin 2 2 1.68
Substituting Eq.(1.65), Eq.(1.66), Eq.(1.67) and Eq.(1.68) into Eq.(1.64), we obtain:
2 2
cos 2 cos csc sin cos cot sin cot sin sin
2
Lˆ2y 2 1.69
2
cot sin cos cot 2 sin cos cot 2 sin 2 2
Finally, the component of angular momentum operator square in y direction is also given by:
Lˆ2z Lˆz Lˆz i i
2
Lˆ2z 2
1.70
2
Square of angular momentum operator in spherical coordinate system can be obtained by
substituting Eq. (1.62), Eq.(1.69) and Eq.(1.70) into Eq.(1.56).
Lˆ2 Lˆ2x Lˆ2y Lˆ2z
2 2
sin 2 sin csc cos sin cot cos cot cos 2
2
2
2
cot cos sin cot 2 cos sin cot 2 cos 2 2 cos 2 2
2 cos csc 2 sin cos cot sin cot sin 2 cot sin cos
cot 2 sin cos cot 2 sin 2
2
2
2 2
16
2 2 2 2
2
sin cos 2
cot sin 2
cot cos 2
cot 2
sin 2
2 2 2 2 2
2
cot 2 cos 2 2
2 2
2
2 2
2
2 2 2 2 2 2 2 2
sin cos cot sin cos cot sin cos
2 2
2
2
2 cot cot 2
2 2
2 2
Lˆ2 2
2 cot 1 cot 2
2 1.71
From trigonometric relation and application of product rule differentiation,
2 1
2 cot sin 1.72
sin
cos2
1 cot 2 1
sin
2
sin 2
cos 2
1
1
sin sin 2
2 1.73
Put Eq.(1.72) and Eq.(1.73) into Eq.(1.71), we obtain the final result:
1 1 2
Lˆ2 2
sin sin sin 2 2 1.74
Individual Assignment
1. From Spherical coordinate system we have
x r sin cos
y r sin sin 1.75
z r cos
Based on Eq.(1.75), the position vector 𝑟 in spherical coordinate is given by:
r xxˆ yyˆ zzˆ
r r sin cos xˆ r sin cos yˆ r cos zˆ 1.76
17
Based on Eq.(1.76),
A. Drive an expression of a unit vector in spherical coordinate (𝑟̂ , 𝜃̂, 𝜙̂)
B. Find the expression of unit vector (𝑥̂, 𝑦̂, 𝑧̂ )in terms of (𝑟̂ , 𝜃̂, 𝜙̂) by using matrix
representation.
rˆ rˆ ˆ ˆ ˆ ˆ
C. Drive the expression for: , , , , ,
Solution
A(i )
rˆ dr
dr dr dr
dr d
r sin cos xˆ r sin sin yˆ r cos zˆ
dr dr
dr
sin cos xˆ sin sin yˆ cos zˆ
dr
dr
sin cos xˆ sin sin yˆ cos zˆ
dr
dr
sin 2 cos 2 sin 2 sin 2 cos 2 , where xˆ xˆ yˆ yˆ zˆ zˆ 1
dr
sin 2 cos 2 sin 2 2 cos 2
sin 2 cos 2
1
rˆ dr
dr dr
dr
sin cos xˆ sin sin yˆ cos zˆ 1.77
ii
ˆ dr d dr d
dr d
r sin cos xˆ r sin sin yˆ r cos zˆ
d d
r cos cos xˆ r cos sin yˆ r sin zˆ
r cos cos xˆ cos sin yˆ sin zˆ
r 2 cos 2 cos 2 cos 2 sin 2 sin 2
dr
d
r cos cos sin sin
2 2 2 2
r cos sin
2 2
r
18
dr d r cos cos x cosr sin y sin z
ˆ ˆ ˆ
ˆ dr d
ˆ cos cos xˆ cos sin yˆ sin zˆ 1.78
iii ˆ dr d dr
d
dr d
r sin cos xˆ r sin sin yˆ r cos zˆ
d d
r sin sin xˆ r sin cos yˆ
r sin sin xˆ sin cos yˆ
r 2 sin 2 sin 2 sin 2 cos 2
dr
d
r sin 2 sin 2 cos 2
r sin 2
r sin
ˆ dr d dr
r sin sin xˆ sin cos yˆ
d
r sin
ˆ sin xˆ cos yˆ 1.79
Therefore, a unit vector in spherical coordinate is:
rˆ sin cos xˆ sin sin yˆ cos zˆ
ˆ cos cos xˆ cos sin yˆ sin zˆ 1.80
ˆ sin xˆ cos yˆ
B, To find the expression of unit vector (𝑥̂, 𝑦̂, 𝑧̂ ) in terms of (𝑟̂ , 𝜃̂ , 𝜙̂), we can represent
Eq.(1.80) in the form of matrix representation follow:
rˆ sin cos sin sin cos xˆ
ˆ
cos cos cos sin sin yˆ 1.81
ˆ sin cos 0 zˆ
19
Spherical to rectangular coordinate transformation is the inverse of the rectangular to
spherical coordinate transformation.
rˆ,ˆ,ˆ xˆ, yˆ, zˆ by using transpose (convert row matrix into column matrix )
1
xˆ sin cos sin sin cos rˆ
yˆ cos cos ˆ
cos sin sin
zˆ sin cos 0 ˆ
xˆ sin cos cos cos sin rˆ
yˆ sin sin
cos sin cos ˆ 1.82
zˆ cos sin 0 ˆ
Therefore, from Eq. (1.82), we obtain:
xˆ sin cos rˆ cos cos ˆ sin ˆ
yˆ sin sin cos sin cos 83
zˆ cos sin
rˆ
C ) i, sin cos xˆ sin cos yˆ cos zˆ
cos cos xˆ cos cos yˆ sin zˆ
ˆ
rˆ
ˆ 1.84
rˆ
ii ) sin cos xˆ sin sin yˆ cos zˆ
sin sin xˆ sin cos yˆ
sin xˆ cos yˆ sin
ˆ
rˆ
ˆ sin 1.85
20
ˆ
iii ) cos cos xˆ cos sin yˆ sin zˆ
sin cos xˆ sin sin yˆ cos zˆ
sin cos xˆ sin sin yˆ cos zˆ
rˆ
ˆ
rˆ 1.86
ˆ
iv) cos cos xˆ cos sin yˆ sin zˆ
cos sin xˆ cos cos yˆ
sin xˆ cos yˆ cos
ˆ
ˆ ˆ
cos 1.87
ˆ
v) sin xˆ cos yˆ
ˆ
0 1.88
ˆ ˆ
vi ) sin xˆ cos yˆ
ˆ
cos xˆ sin yˆ rˆ sin ˆ cos 1.89
1.4. Commutation rules
The component of angular momentum operators satisfy the following commutation relations:
xˆ, pˆ x yˆ , pˆ y zˆ, pˆ z i
1.90
pˆ x , xˆ pˆ y , yˆ pˆ z , zˆ i
We begin by writing each angular momentum operators in terms of the position
and linear momentum and using the fact that:
i) A, BC A, B C B A, C 1.91
21
ii) AB, C A B, C A, C B 1.92
iii) AB, CD AB, C D C AB, D 1.93
AB, CD A B, C D A, C BD CA B, D C A, D B 1.94
iv) A B, C D A, C A, D B, C B, D 1.95
1.4.1. Position- Angular momentum operator commutation relation
1. Prove that xˆ, Lˆx 0
xˆ, Lˆx xˆ, yp ˆ ˆ y
ˆ ˆ z zp
xˆ, yp
ˆˆ z xˆ, zp
ˆ ˆ y ,applying by Eq. 1.91
xˆ, yˆ pˆ z yˆ xˆ, pˆ z xˆ, zˆ pˆ y zˆ xˆ, pˆ y
0 0 0 0
xˆ, Lˆx 0
1.96
Exercise 1
I. Show that:
A) yˆ , Lˆ y 0
B) zˆ, Lˆz 0
2. Show that the xˆ, Lˆ y i zˆ
xˆ, Lˆ y xˆ , zp ˆˆ z
ˆ ˆ x xp
xˆ, zp
ˆ ˆ x xˆ , xp
ˆˆ z
xˆ, zˆ pˆ x zˆ xˆ , pˆ x xˆ , xˆ pˆ z xˆ xˆ , pˆ z
0 i 0 0
xˆ, Lˆ y i zˆ
1.97
22
Prove that
A. [𝑦̂, 𝐿̂𝑦 ] = 𝑖ℏ𝑥̂ and [𝐿̂𝑦 , 𝑦̂] = −𝑖ℏ𝑥̂
B. [𝑧̂ , 𝐿̂𝑥 ] = 𝑖ℏ𝑦̂ and [𝐿̂𝑥 , 𝑧̂ ] = −𝑖ℏ𝑦̂
3. Shaw that Lˆx , yˆ i zˆ
Lˆx , yˆ yp
ˆˆ ˆ ˆ ˆ
z zp y , y
yp
ˆˆ z , yˆ zp
ˆ ˆ y , yˆ , byapplying Eq.(1.92) AB, C A B, C A, C B
yˆ pˆ z , yˆ yˆ , yˆ pˆ z zˆ pˆ y , yˆ zˆ, yˆ pˆ y
0 0 i 0
ẑ i
Lˆx , yˆ i zˆ
1.98
Exercise 2
II. Prove that:
A. [𝐿̂𝑦 , 𝑧̂ ] = 𝑖ℏ𝑥 ̂
B. [𝐿̂𝑧 , 𝑥̂] = 𝑖ℏ𝑦̂
1.4.2. Momentum angular momentum operator commutation relation
1) pˆ x , Lˆx pˆ x , yp ˆ ˆ y
ˆ ˆ z zp
pˆ x , yp
ˆˆ z pˆ x , zp
ˆ ˆ y
pˆ x , yˆ pˆ z yˆ pˆ x , pˆ z pˆ x , zˆ pˆ y zˆ pˆ x , pˆ y
0 0 0 0
pˆ x , Lˆx 0
1.99
2) pˆ x , Lˆ y pˆ x , zp ˆˆ z
ˆ ˆ x xp
pˆ x , zp
ˆ ˆ x pˆ x , xp
ˆˆ z
pˆ x , zˆ pˆ x zˆ pˆ x , pˆ x pˆ x , xˆ pˆ z xˆ pˆ x , pˆ z
0 0 i 0
i pˆ z
23
pˆ x , Lˆ y i pˆ z
1.100
Exercise 3
III. Prove that:
A. [𝑝̂𝑦 , 𝐿̂𝑧 ] = 𝑖ℏ𝑝̂𝑥
B. [𝑝̂𝑧 , 𝐿̂𝑥 ] = 𝑖ℏ𝑝̂𝑦
Remark!
i) pˆ x , Lˆx pˆ y , Lˆ y pˆ z , Lˆz 0
1.101
ii) pˆ x , Lˆ y i pˆ z , Lˆx , pˆ y i pˆ z 1.102
iii) pˆ y , Lˆz i pˆ x , Lˆ y , pˆ z i pˆ x 1.103
iv) pˆ z , Lˆx i pˆ y , Lˆz , pˆ x i pˆ y 1.104
1.4.3. Angular momentum - angular momentum commutation relation
Let find out whether 𝐿̂𝑥 , 𝐿̂𝑦 , 𝐿̂𝑧 operators commute or not.
In so doing, we star with:
Lˆx , Lˆx Lˆ y , Lˆ y Lˆz , Lˆz 0
1.105
Example
1. Show that [𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ℏ𝐿̂𝑧
Solution
Lˆx , Lˆ y yp
ˆˆ ˆ ˆ ˆ ˆ ˆˆ
z zp y , zpx xpz , applying Eq.(1.95)
yp ˆ ˆ x yp
ˆ ˆ z , zp ˆˆ z zp
ˆ ˆ z , xp ˆ ˆ x zp
ˆ ˆ y , zp ˆˆ z
ˆ ˆ y , xp 1.106
I II III IV
24
I yp ˆ ˆ x wecan re writein theformof AB, C
ˆˆ z , zp
yp
ˆˆ z , zˆ pˆ x zˆ yp
ˆˆ z , pˆ x
yˆ pˆ z , zˆ pˆ x yˆ , zˆ pˆ z pˆ x zy
ˆ ˆ pˆ z , pˆ x zˆ yˆ , pˆ x pˆ z
i 0 0 0
I i yp
ˆˆ x 1.107
II yp ˆˆ z
ˆˆ z , xp
yp
ˆˆ z , xˆ pˆ z xˆ yp
ˆˆ z , pˆ z
yˆ pˆ z , xˆ pˆ z yˆ , xˆ pˆ z pˆ z xy
ˆˆ pˆ z , pˆ z xˆ yˆ , pˆ z pˆ z
0 0 0 0
II 0 1.108
III zp ˆ ˆ x
ˆ ˆ y , zp
zp
ˆ ˆ y , zˆ pˆ x zˆ zp
ˆ ˆ y , pˆ x
zˆ pˆ y , zˆ pˆ x zˆ, zˆ pˆ y pˆ x zz
ˆˆ pˆ y , pˆ x zˆ zˆ, pˆ x pˆ y
0 0 0 0
III 0 1.109
IV zp ˆˆ z
ˆ ˆ y , xp
zp
ˆ ˆ y , xˆ pˆ z xˆ zp
ˆ ˆ y , pˆ z
zˆ pˆ y , xˆ pˆ z zˆ, xˆ pˆ y pˆ z xz
ˆ ˆ pˆ y , pˆ z xˆ zˆ, pˆ z pˆ y
0 0 0 i
IV i xp
ˆˆ y 1.110
Put Eq.(1.107), Eq.(1.108), Eq.(1.109) and Eq.(1.110) into Eq.(1.106), we obtain:
Lˆx , Lˆ y I II III IV
i ypˆˆ x 0 0 i xp
ˆˆ y
i yp
ˆˆ x i xp
ˆˆ y
i xp
ˆˆ y i yp
ˆˆ x
i xp
ˆˆ y
ˆˆx
yp
Lˆz
Lˆx , Lˆ y i Lˆz
1.111
25
By another method (trick):
Lˆx , Lˆ y yp
ˆ ˆ ˆ ˆ ˆ ˆ ˆˆ
z zp y , zpx xpz
yp ˆ ˆ x yp
ˆ ˆ z , zp ˆˆ z zp
ˆ ˆ z , xp ˆ ˆ x zp
ˆ ˆ y , zp ˆˆ z
ˆ ˆ y , xp
ˆ ˆ x pˆ z , zˆ yx
yp ˆ ˆ pˆ z , pˆ z pˆ y pˆ x zˆ, zˆ xp
ˆˆ y zˆ, pˆ z
i 0 0 i
i yp
ˆ ˆ x i xp
ˆˆ y
i xp
ˆˆ y i yp
ˆˆx
i xˆˆp y
ˆˆx
yp
Lˆz
Lˆx , Lˆ y i Lˆz
Exercise 4
1. By applying similar procedures; show that the cyclic permutation of indices given as:
A. [𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝑖ℏ𝐿̂𝑥
B. [𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝑖ℏ𝐿̂𝑦
26
Figure 2: Clockwise and anti-clockwise rotation (cyclic permutation of indices) of angular
momentum operator
From above Figure,
xˆ xˆ o xˆ yˆ zˆ Lˆx Lˆ y i Lˆ y
yˆ yˆ 0 yˆ zˆ xˆ Lˆ y Lˆz i Lˆx anti-clockwise direction 1.112
zˆ zˆ 0 zˆ xˆ yˆ Lˆz Lˆx i Lˆz
xˆ xˆ o yˆ xˆ zˆ Lˆ y Lˆx i Lˆ y
yˆ yˆ 0 zˆ yˆ xˆ Lˆz Lˆ y i Lˆx clockwise direction 1.113
zˆ zˆ 0 xˆ zˆ yˆ Lˆx Lˆz i Lˆz
Remark!
We conclude that any two component of angular momentum do not commute, which means
that their corresponding observable cannot be measured simultaneously i.e., 𝐿̂𝑥 , 𝐿̂𝑦 𝑎𝑛𝑑 𝐿̂𝑧 are
in compactable observable.
27
Example
1. Show that every component of angular momentum operator commutes with 𝐿̂2 .
Solution
i) Lˆ2 , Lˆx Lˆ2x Lˆ2y Lˆ2z , Lˆx
Lˆ2x , Lˆx Lˆ2y , Lˆx Lˆ2z , Lˆx , we applyin the formof AB, C
Lˆx Lˆx , Lˆx Lˆ y Lˆ y , Lˆx Lˆz Lˆz , Lˆx , we apply cyclic permutation
Lˆx Lˆx , Lˆx Lˆx , Lˆx Lˆx Lˆ y Lˆ y , Lˆx Lˆ y , Lˆx Lˆ y Lˆz Lˆz , Lˆx Lˆz , Lˆx Lˆz
0 0 i Lˆz i Lˆz i Lˆ y i Lˆ y
Lˆ y i Lˆz i Lˆz Lˆ y Lˆz i Lˆ y i Lˆ y Lˆz
i Lˆ y Lˆz i Lˆz Lˆ y i Lˆ y Lˆz i Lˆ y Lˆz
i Lˆ y Lˆz Lˆz Lˆ y Lˆ y Lˆz Lˆ y Lˆz
i 0
Lˆ2 , Lˆx 0
1.114
ii) Lˆ2 , Lˆ y Lˆ2x Lˆ2y Lˆ2z , Lˆ y
Lˆ2x , Lˆ y Lˆ2y , Lˆ y Lˆ2z , Lˆ y
0
Lˆ2x , Lˆ y Lˆ2z , Lˆ y
Lˆx Lˆx , Lˆ y Lˆz Lˆz , Lˆ y ,
Lˆx Lˆx , Lˆ y Lˆx , Lˆ y Lˆx Lˆz Lˆz , Lˆ y Lˆz , Lˆ y Lˆz ,
i Lˆz i Lˆz i Lˆx i Lˆx
28
Lˆx i Lˆz i Lˆz Lˆx Lˆz i Lˆx i Lˆx Lˆz
i Lˆx Lˆz i Lˆz Lˆx i Lˆz Lˆx i Lˆx Lˆz
i Lˆx Lˆz Lˆz Lˆx Lˆz Lˆx Lˆx Lˆz
i 0
Lˆ2 , Lˆ y 0
1.115
ii) Lˆ2 , Lˆz Lˆ2x Lˆ2y Lˆ2z , Lˆz
Lˆ2x , Lˆz Lˆ2y , Lˆz Lˆ2z , Lˆz
0
Lˆ2x , Lˆz Lˆ2y , Lˆz
Lˆx Lˆx , Lˆz Lˆ y Lˆ y , Lˆz ,
Lˆx Lˆx , Lˆz Lˆx , Lˆz Lˆx Lˆ y Lˆ y , Lˆz Lˆ y , Lˆz Lˆ y ,
i Lˆ y i Lˆ y i Lˆx i Lˆx
Lˆx i Lˆ y i Lˆ y Lˆx Lˆ y i Lˆx i Lˆx Lˆ y
i Lˆx Lˆ y i Lˆ y Lˆx i Lˆ y Lˆx i Lˆx Lˆ y
i Lˆx Lˆ y Lˆ y Lˆx Lˆ y Lˆx Lˆx Lˆ y
i 0
Lˆ2 , Lˆz 0
1.116
1.5. Eigen value of 𝑳̂𝒛 and 𝑳̂𝟐
In Quantum mechanics, there are two types of angular momentum:
Orbital angular momentum ( 𝐿̂ ) and
Spin angular ( 𝑆̂)
Generalized angular momentum ( 𝐽̂ ) is the combination of 𝐿̂ + 𝑆̂.
29
Angular momentum is quantized.
State of orbital angular momentum are characterized by two quantum numbers:
𝑙, the orbital quantum number and
𝑚, the azimuthal or magnetic quantum number.
The magnitude of angular momentum operator square is given by the discrete set of value
of:
Lˆ2 2
l l 1 , l 0,1, 2,3,... 1.117
The magnitude of angular momentum component ( 𝐿̂𝑧 ) is given by the discrete set of
value of:
Lˆz m , m l , l 1,... l 1, l 1.118
In the case of orbital angular momentum, both 𝑙 and 𝑚 are integers.
The system is quantized, so only specific values of angular momentum are ever measured.
Table 1: shows s few values of 𝑙 𝑎𝑛𝑑 𝑚
Orbital Quantum Angular Possible values of 𝑚 # (total number)
number ( 𝑙 ) momentum (𝐿̂)
0 0 0 1
1 ℏ√2 -1, 0, 1 3
2 ℏ√6 -2, -1, 0, 1, 2 5
3 ℏ√12 -3, -2, -1, 0, 1, 2, 3 7
Since 𝐿̂𝑧 and 𝐿̂2 commute, they have common eigenstates.
30
We learn that the operators 𝐿̂2 commutes with any component of 𝐿̂, then we find
simultaneous eigenstate of 𝐿̂2 and component of 𝐿̂.
Denoting the common eigenstate by |𝜆, 𝑚⟩, one can write ;
Lˆz , m m , m 1.119
And
Lˆ2 , m 2
, m 1.120
In order to determine the value of 𝑚 and 𝜆, we have to use ladder operator techniques (to
find the eigenvalue of 𝐿̂𝑧 and 𝐿̂2 )
Raising and lowering operator (step up and step down operator) or ladder operator
The step-up operator is defined by
Lˆ Lˆx iLˆ y 1.121
The step-down operator is defined as the adjoint of the step-up operator:
Lˆ
†
Lˆ Lˆ
Lˆ iLˆ
x y
Lˆ Lˆx iLˆ y 1.122
Notice that:
1
2
Lˆ 1
2
1
Lˆ Lˆx iLˆ y Lˆx iLˆ y 2 Lˆx Lˆx
2
1.123
1
2i
Lˆ Lˆ
1
2i
Lˆx iLˆ y Lˆx iLˆ y
1
2i
2iLˆ y Lˆ y 1.124
I. 𝐿̂+ and 𝐿̂− satisfy the following commutation relation with 𝐿̂𝑧 :
A) Lˆz , Lˆ Lˆz , Lˆx iLˆ y
Lˆz , Lˆx i Lˆz , Lˆ y
31
Lˆz , Lˆx i Lˆz , Lˆ y
i Lˆ y i Lˆx
i Lˆ y i i Lˆx
i Lˆ y i 2 Lˆx , i 2 1
i Lˆ y Lˆx
Lˆx i Lˆ y
Lˆ iLˆ
x y
Lˆ
Lˆz , Lˆ Lˆ
1.125
Lˆz , Lˆ Lˆz Lˆ Lˆ Lˆz Lˆ
Lˆz Lˆ Lˆ Lˆz Lˆ 1.126
B) Lˆz , Lˆ Lˆz , Lˆx iLˆ y
Lˆz , Lˆx i Lˆz , Lˆ y
Lˆz , Lˆx i Lˆz , Lˆ y
i Lˆ y i Lˆ x
i Lˆ y i i Lˆx
i Lˆ y i 2 Lˆx , i 2 1
i Lˆ y Lˆx
Lˆx i Lˆ y
Lˆ x iLˆ y
Lˆ
Lˆz , Lˆ Lˆ
Lˆz , Lˆ Lˆz Lˆ Lˆ Lˆ z Lˆ 1.127
Lˆ Lˆ Lˆ Lˆ Lˆ
z z 1.128
Consider the action of Eq.(1.126) on an Eigen state |𝜆, 𝑚⟩
32
Lˆz Lˆ , m Lˆ Lˆz Lˆ , m , where Lˆz m
m Lˆ Lˆ , m
Lˆ Lˆ , m m 1 Lˆ , m
z 1.129
From Eq.(1.129), Lˆ , m is an eigen state of 𝐿̂𝑧 with an eigenvalue of m 1
Eq.(1.129) can be written as:
Lˆ , m C , m 1 1.130
Where 𝐶+ is a constant to be determined.
We note that 𝐿̂+ has the effect of increasing the eigenvalue 𝑚 by 1(one), unless
𝐿̂+ |𝜆, 𝑚⟩ = 0.
For this reason, 𝐿̂+ is called a raising (step-up) operator.
Take the action of Eq.(1.128) on an eigen state |𝜆, 𝑚⟩:
Lˆz Lˆ , m Lˆ Lˆz Lˆ , m , where Lˆz m
m Lˆ
Lˆ , m
Lˆz Lˆ , m m 1 Lˆ , m 1.131
Since Lˆ , m is an Eigen state of 𝐿̂𝑧 with an eigenvalue m 1 .
One can write Eq.(1.131) as:
Lˆ , m C , m 1 1.132
Where 𝐶− is a constant to be determined.
The effect of 𝐿̂− is to decrease the eigenvalue of 𝑚 by 1(one), unless 𝐿̂− |𝜆, 𝑚⟩ = 0.
For this reason, 𝐿̂− is called lowering (step-down) operator.
II. The operator 𝐿̂+ and 𝐿̂+ also commute with the angular momentum squared.
Lˆ2 , Lˆ 0
1.133
33
We have:
Lˆ2 Lˆ , m Lˆ Lˆ2 , m 2
Lˆ
, m 1.134
So that the state generated by the action of 𝐿̂± are still Eigen states of 𝐿̂2 belonging to the
same eigenvalue 𝜆ℏ2 .
Lˆ , m C , m 1 1.135
Lˆ , m C , m 1 1.136
Where 𝐶± are constants of proportionality.
For a given 𝜆, 𝑚2 ≤ 𝜆, so that 𝑚 must have both a maximum value, 𝑚𝑚𝑎𝑥 and a minimum
value, 𝑚𝑚𝑖𝑛 .
Lˆ2 Lˆ2x Lˆ2y Lˆ2z
Lˆ2 Lˆ2z Lˆ2x Lˆ2y 1.137
Take the action of Eq.(1.137) on the Eigen state |𝜆, 𝑚⟩:
Lˆ Lˆ , m Lˆ Lˆ , m , where
2 2
z
2
x
2
y Lˆ2 2
and Lˆ2z m
2
m , m Lˆ Lˆ , m
2 2 2 2
x
2
y
m , m Lˆ Lˆ , m
2 2 2
x
2
y 1.138
Taking the scalar (inner) product of Eq.(1.139), we obtain:
, m m2 2
, m , m Lˆ2x Lˆ2y , m
m 2 2
Lˆ2x Lˆ2y 0
m 2 2
0 or m 1.139
To proceed further, one can express 𝐿̂2 in terms of 𝐿̂+ and 𝐿̂− and ̂𝐿𝑧 .
a) Lˆ Lˆ Lˆx iLˆ y Lˆ iLˆ
x y
Lˆ2x iLˆx Lˆ y iLˆ y Lˆx i 2 Lˆ2y , i 2 1
Lˆ2x iLˆx Lˆ y iLˆ y Lˆx Lˆ2y
Lˆ2x Lˆ2y iLˆx Lˆ y iLˆ y Lˆx
34
Lˆ2x Lˆ2y i Lˆx Lˆ y Lˆ y Lˆx
Lˆx , Lˆ y
Lˆ2x Lˆ2y i Lˆx , Lˆ y
i Lˆz
Lˆ2x Lˆ2y i i Lˆz
Lˆ2x Lˆ2y i 2 Lˆz , i 2 1
Lˆ Lˆ Lˆ2x Lˆ2y Lˆz 1.140
Put Eq.(1.137) into Eq.(1.140), we obtain:
Lˆ Lˆ Lˆ2x Lˆ2y Lˆz
Lˆ2 Lˆ2z
Lˆ2 Lˆ Lˆ Lˆz Lˆ2z 1.142
Lˆ Lˆ Lˆ2 Lˆ2z Lˆz 1.141
b) Lˆ Lˆ Lˆx iLˆ y Lˆ iLˆ
x y
Lˆ2x iLˆx Lˆ y iLˆ y Lˆx i 2 Lˆ2y , i 2 1
Lˆ2x iLˆx Lˆ y iLˆ y Lˆx Lˆ2y
Lˆ2x Lˆ2y iLˆx Lˆ y iLˆ y Lˆx
Lˆ2x Lˆ2y i Lˆx Lˆ y Lˆ y Lˆx
Lˆx , Lˆ y
Lˆ2x Lˆ2y i Lˆx , Lˆ y
i Lˆz
Lˆ2x Lˆ2y i i Lˆz
Lˆ2x Lˆ2y i 2 Lˆz , i 2 1
Lˆ Lˆ Lˆ2x Lˆ2y Lˆz 1.143
35
Put Eq.(1.137) into Eq.(1.143), we obtain:
Lˆ Lˆ Lˆ2x Lˆ2y Lˆz
Lˆ2 Lˆ2z
Lˆ Lˆ Lˆ2 Lˆ2z Lˆz 1.144
Lˆ2 Lˆ Lˆ Lˆz Lˆ2z 1.145
Applying Eq.(1.145) to the state of minimum, 𝑚𝑚𝑖𝑛 , we find:
L2 , mmin Lˆ Lˆ Lˆz Lˆ2z , mmin
0 mmin z mmin , mmin
2
mmin 2
mmin
2 2
, m min
mmin
2 2
mmin 2
, m min
L , mmin mmin mmin 1
2 2
, mmin 1.146
Thus, we deduced that from Eq.(1.146):
mmin mmin 1 1.147
Similarly, applying Eq.(1.142) to the state of maximum, 𝑚𝑚𝑎𝑥 , we find:
L2 , mmax Lˆ Lˆ Lˆz Lˆ2z , mmax
0 mmax z mmax , mmax
2
mmax 2
mmax
2 2
, m max
mmax
2 2
mmax 2
, m max
mmax mmax 1 2
, mmax
L2 , mmin mmax mmax 1 2
, mmax 1.148
Thus we deduced that:
mmax mmax 1 1.149
Comparing Eq.(1.149) with Eq.(1.147), we obtain:
mmax mmax 1 mmin mmin 1
mmax mmax 1 mmin mmin 1 1.150
36
By definition, 𝑚𝑚𝑎𝑥 is denoted by 𝑙 and so we write Eq.(1.150) as:
l l 1 mmin mmin 1
l 2 l mmin
2
mmin
2
mmin mmin l 2 l 0 1.151
When we factorized Eq.(1.151), we obtain:
mmin l mmin l 1 0
mmin l 0 and mmin l 1 0 1.152
Since 𝑚𝑚𝑖𝑛 ≤ 𝑙 by definition, the only acceptable root is:
mmin l 0
mmin l mmin mmax 1.153
Since 𝑚𝑚𝑎𝑥 and 𝑚𝑚𝑖𝑛 differ by some integer n, we can write:
mmax mmin n, n 0,1, 2,3...
l l n
l l n
2l n
n
l , n 0,1, 2,3... 1.154
2
So, that the allowed values of 𝑙 are
1 3
l 0, ,1, , 2,... 1.155
2 2
For a give value of 𝑙, the value of 𝑚 ranges:
m l , l 1, , l 1, l 1.156
Hence the eigenvalue of 𝐿̂2 is given by:
mmax mmax 1 , where mmax l
l l 1 1.157
The eigenvalues of 𝐿̂2 and 𝐿̂𝑧 corresponding to the joint eigenvectors |𝑙, 𝑚⟩ are given
respectively, by 𝑙ℏ2 (𝑙 + 1) and ℏ𝑚.
Since 𝜆 = 𝑙(𝑙 + 1), we can equally we label the simultaneous Eigen states of 𝐿̂2 and 𝐿̂𝑧 by
𝑙 rather than by 𝜆 so that:
Lˆ2 l , m 2
l l 1 l , m 1.158
And
37
Lˆz l , m m l , m 1.159
We need to determine the constant of proportionality 𝐶± that appear in the Eq.(1.135) and
Eq.(1.136) by using normalization condition by replacing eigenvector 𝜆 by 𝑙.
i) Lˆ l , m C l , m 1 1.160
ii) Lˆ l , m C l , m 1 1.161
Take the inner product of Eq. (1.160):
C
† †
Lˆ l , m Lˆ , m C , m 1
l, m 1
, l Lˆ† Lˆ , m CC , m 1 l , m 1 , Lˆ† Lˆ
, l Lˆ Lˆ , m CC l , m 1 l , m 1
2
C 1
C l , m Lˆ Lˆ l , m 1.162
2
Substituting Eq. (1.141), into Eq. (1.162), we obtain:
C l , m Lˆ2 Lˆ2z Lˆz l , m , Lˆ Lˆ Lˆ2 Lˆ2z Lˆ z
2
l , m l l 1 2
m
2
m l, m
l , m l l 1 2
m2 l, m 2
m 2
l , m l l 1 m m 1 l , m
2 2
l , m l l 1 m m 1 2
l, m
l l 1 m m 1 2
l, m l, m
1
l l 1 m m 1 2
C l l 1 m m 1 2
C l l 1 m m 1 1.163
Put Eq. (1.163) into Eq.(1.160), we obtain:
Lˆ l , m l l 1 m m 1 l , m 1
1.164
Again we take the inner (scalar) product of Eq. (1.161):
Lˆ C
† †
l, m Lˆ , m C , m 1 l, m 1
, l Lˆ† Lˆ , m CC , m 1 l , m 1 , Lˆ† Lˆ
, l Lˆ Lˆ , m CC l , m 1 l , m 1
2
C 1
38
, l Lˆ Lˆ , m C
2
C l , m Lˆ Lˆ l , m 1.165
2
Put Eq. (1.144) into Eq.(1.165), we obtain:
C l , m Lˆ2 Lˆ2z Lˆz l , m , Lˆ Lˆ Lˆ2 Lˆ2z Lˆ z
2
l , m l l 1 2
m
2
m l, m
l , m l l 1 2
m2 l, m 2
m 2
l , m l l 1 m m 1 l , m
2 2
l , m l l 1 m m 1 2
l, m
l l 1 m m 1 2
l, m l, m
1
l l 1 m m 1 2
C l l 1 m m 1 2
C l l 1 m m 1 1.166
Put Eq. (1.166) into Eq.(1.161), we obtain:
Lˆ l , m l l 1 m m 1 l , m 1 1.167
Which in turn leads to the two relations based on Eq. (1.123) and Eq. (1.124):
1
Lˆx l , m Lˆ Lˆ l , m
2
1 ˆ 1
L l , m Lˆ l , m , but Lˆ l , m l l 1 m m 1 l , m 1
2 2
Lˆ l , m l l 1 m m 1 l , m 1
l l 1 m m 1 l , m 1 l l 1 m m 1 l , m 1
2 2
Lˆx l , m l l 1 m m 1 l , m 1 l l 1 m m 1 l , m 1 1.168
2 2
39
And
Lˆ y l , m
1 ˆ
2i
L Lˆ l , m
1 ˆ 1
L l , m Lˆ l , m , but Lˆ l , m l l 1 m m 1 l , m 1
2i 2i
Lˆ l , m l l 1 m m 1 l , m 1
Lˆ y l , m l l 1 m m 1 l , m 1 l l 1 m m 1 l , m 1
2i 2i
Lˆ y l , m l l 1 m m 1 l , m 1 l l 1 m m 1 l , m 1 1.169
2i
Example
1. Find the expectation value of 𝐿̂𝑥 , 𝐿̂𝑦 and 𝐿̂𝑧 in the state |𝑙, 𝑚⟩
Given Required
𝐿̂𝑥 |𝑙, 𝑚⟩ A) ⟨𝐿𝑥 ⟩ =?
𝐿̂𝑦 |𝑙, 𝑚⟩ B) ⟨𝐿𝑦 ⟩ =?
𝐿̂𝑧 |𝑙, 𝑚⟩⟩ C) ⟨𝐿𝑧 ⟩ =?
Solution
A) Lˆx l , m Lˆx l , m , since Lˆx
2
1 ˆ
L Lˆ
1
l, m Lˆ Lˆ l , m
2
1 1
l, m Lˆ l , m l , m Lˆ l , m , but Lˆ l , m l l 1 m m 1 l , m 1
2 2
Lˆ l , m l l 1 m m 1 l , m 1
1 1
l, m l l 1 m m 1 l , m 1 l, m l l 1 m m 1 l , m 1
2 2
l l 1 m m 1 l , m l , m 1 l l 1 m m 1 l , m l , m 1
2 2
0 0
00
40
Lˆx 0 1.170
B) Lˆ y l , m Lˆ y l , m , since Lˆ y
1 ˆ
2i
L Lˆ
1
l , m Lˆ Lˆ l , m
2i
1 1
l , m Lˆ l , m l , m Lˆ l , m , but Lˆ l , m l l 1 m m 1 l , m 1
2i 2i
Lˆ l , m l l 1 m m 1 l , m 1
1 1
l, m l l 1 m m 1 l , m 1 l, m l l 1 m m 1 l , m 1
2i 2i
l l 1 m m 1 l , m l , m 1 l l 1 m m 1 l , m l , m 1
2i 2i
0 0
00
Lˆ y 0 1.171
C ) Lˆz l , m Lˆz l , m , since Lˆ y m
l, m m l, m
m l, m l, m
1
Lˆz m 1.172
2. Find the expectation value of 𝐿̂2𝑥 , 𝐿̂2𝑦 and 𝐿̂2𝑧 in the state |𝑙, 𝑚⟩
Given Required
𝐿̂2𝑥 |𝑙, 𝑚⟩ A) ⟨𝐿̂2𝑥 ⟩ =?
𝐿̂2𝑦 |𝑙, 𝑚⟩ B) ⟨𝐿̂2𝑦 ⟩ =?
𝐿̂2𝑧 |𝑙, 𝑚⟩⟩ C) ⟨𝐿̂2𝑧 ⟩ =?
41
Solution
2
Lˆ Lˆ 1
A) Lˆ2x l , m Lˆ2x l , m , since Lˆ2x
2
Lˆ Lˆ Lˆ
1
Lˆ Lˆ2 Lˆ Lˆ Lˆ Lˆ Lˆ2
4 4
l, m
4
1 ˆ2 ˆ ˆ
L L L Lˆ Lˆ Lˆ2 l , m
1 1 1 1
l , m Lˆ2 l , m l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m l , m Lˆ2 l , m , but Lˆ2 l , m C l , m 2
4 4 4 4
Lˆ2 l , m C ' l , m 2
1 1 1 1
C l , m l , m 2 l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m C ' l , m l , m 2
4 4 4 4
0 0
1 1
l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m ,but Lˆ Lˆ Lˆ2 Lˆ2z Lˆz and Lˆ Lˆ Lˆ2 Lˆ2z Lˆ z
4 4
1 1
l , m Lˆ2 Lˆ2z Lˆz l , m l , m Lˆ2 Lˆ2z Lˆz l , m
4 4
1 1
l , m l l 1 m m l, m l , m l l 1 m m l, m
2 2 2 2
4 4
1
4
l l 1 2
m2 2
m 2
l, m l, m
1
4
l l 1 2
m2 2
m 2
l, m l, m
1 1
1
4
l l 1 2
m2 2
m 2
14 l l 1 2
m2 2
m 2
2 2
4
l l 1 m 4 l l 1 m
2 2
2 2
l l 1 m2
4
2
Lˆ2y l l 1 m2 1.173
2
2
Lˆ2x Lˆ2y l l 1 m2 1.174
2
42
2
Lˆ Lˆ
B ) Lˆ2y l , m Lˆ2y l , m , since Lˆ2y
1
Lˆ Lˆ Lˆ 1
Lˆ Lˆ2 Lˆ Lˆ Lˆ Lˆ Lˆ2
2i 4 4
4
1 ˆ2 ˆ ˆ
L L L Lˆ Lˆ Lˆ2
l, m
1 ˆ2 ˆ ˆ
4
L L L Lˆ Lˆ Lˆ2 l , m
1 1 1 1
l , m Lˆ2 l , m l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m l , m Lˆ2 l , m , but Lˆ2 l , m C l , m 2
4 4 4 4
Lˆ2 l , m C ' l , m 2
1 1 1 1
C l , m l , m 2 l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m C ' l , m l , m 2 , due to orthogonality
4 4 4 4
0 0
1 1
l , m Lˆ Lˆ l , m l , m Lˆ Lˆ l , m , but Lˆ Lˆ Lˆ2 Lˆ2z Lˆ z and Lˆ Lˆ Lˆ2 Lˆ2z Lˆ z
4 4
1 1
l , m Lˆ2 Lˆ2z Lˆz l , m l , m Lˆ2 Lˆ2z Lˆ z l , m
4 4
1 1
l , m l l 1 2 m m l , m l , m l l 1 2 m m l , m
2 2
4 4
l l 1 2 m 2 2 m 2 l , m l , m l l 1 2 m 2 2 m 2 l , m l , m
1 1
4 4
1 1
1
4
l l 1 2
m2 2
m 2
1
l l 1
4
2
m2 2
m 2
2 2
4
l l 1 m 4 l l 1 m
2 2
2 2
l l 1 m 2
4
2
Lˆ2y l l 1 m 2 1.175
2
C ) Lˆ2z l , m Lˆ2z l , m , since Lˆ2z m m2
2 2
l , m m2 2
l, m
m2 2
l, m l, m
1
Lˆ2z m2 2
1.176
43
The uncertainty Relations for Angular momentum
The generalized uncertainty relation for two operators 𝐴̂ and 𝐵̂ is given by
2
Aˆ , Bˆ
Aˆ Bˆ
2 2
2i
Aˆ , Bˆ
ˆ ˆ
A B
2i
1.177
We can write down uncertainty relations for the components of angular momentum operator
using the commutation relations as follows:
Lˆx , Lˆ y i Lˆz
i ˆ
Lˆx Lˆ y Lz Lˆz 1.178
2i 2i 2i 2
Example
1. For a state of angular momentum |𝑙, 𝑚⟩
A. Show that ∆𝐿̂𝑧 = 0
ℏ 2𝑚
B. Show that ∆𝐿̂𝑥 ∆𝐿̂𝑦 =
2
C. Show that ∆𝐿̂𝑥 ∆𝐿̂𝑧 = 0
Solution
A. Since |𝑙, 𝑚⟩ is an Eigen state of 𝐿̂𝑧 , the expectation value of 𝐿̂𝑧 is
Lˆz l. m Lˆz l. m , Lˆz m
l. m m l. m
m l. m l , m
1
Lˆz m
44
Lˆ2z l. m Lˆ2z l. m , Lˆ2z m 2 2
l. m m 2 2
l. m
m2 2
l. m l , m
Lˆ2z m 2 2
Standard deviation of momentum or uncertainty of momentum operator 𝐿̂𝑧 is
2
Lˆz Lˆ2z Lˆz
m
2
m2 2
m2 2
m2 2
Lˆz 0 1.179
Lˆx , Lˆ y i Lˆz
i ˆ
B) Lˆx Lˆ y Lz
2i 2i 2i
Lˆz , but Lˆz m
2
m
2
2
m
1.180
2
Lˆx , Lˆz i Lˆz
i
C) Lˆx Lˆz Lˆz Lˆz , but Lˆz 0
2i 2i 2i 2
Lˆx Lˆz 0 1.181
Exercise
1. Show that:
A. [𝐿̂+ , 𝐿̂− ] = 2ℏ𝐿̂𝑧
B. [𝐿̂− , 𝐿̂+ ] = 2ℏ𝐿̂𝑧
45
1.6. Eigen function of angular momentum operator
We know that the joint Eigen state of 𝐿̂𝑧 and 𝐿̂2 denoted by |𝑙, 𝑚⟩ is
Lˆ2 l , m 2
l l 1 l , m 1.182
Lˆz l , m m l , m 1.183
And
The operators 𝐿̂𝑧 and 𝐿̂2 can be expressed in terms of spherical coordinate is given by
2
Lˆz i 1.184
2
1 1 2
Lˆ2 2
sin 2 1.185
sin sin
2
Since the operator 𝐿̂𝑧 and 𝐿̂2 are depending only on the angles 𝜃 and 𝜙 which Eigen states is
also depending only on 𝜃 and 𝜙.
Denoting their eigenvectors by ⟨𝜃, 𝜙|𝑙, 𝑚⟩
, l , m Yl , m , Yl m , Spherical hharmonics 1.186
l , m Yl , m Yl m 1.187
We can rewrite the eigenvalue equation of the spherical harmonic of Eq. (1.182) and Eq.
(1.183) as :
Lˆ2Yl , m , 2
l l 1 Yl , m , 1.188
LˆzYl , m , m Yl , m , 1.189
Remark!
The simultaneous Eigen functions of 𝐿2 and 𝐿̂𝑧 are called spherical harmonics.
They are designated by Yl , m , .
We decompose the Eigen functions Yl , m , into a product of a function 𝜃 and a function 𝜙
as follow:
Yl , m , Θl , m Φm 1.190
46
Eigen function and eigenvalue of 𝑳̂𝒛
From Eq. (1.189), we have:
LˆzYl , m , m Yl , m , ,since Yl , m , Θl , m Φm
Lˆz Θl , m Φm m Θl , m Φm , since Lˆz i
i Θl , m Φm m Θl , m Φm
i Φm mΦm
d
i Φm mΦm
d
d
Φm imΦm
d
dΦm imd Φm
dΦm
imd 1.191
Φ m
Integrating both side of Eq.(1.191), we obtain:
dΦ m
Φ m
imd
dΦ m
Φ m
im d
ln Φ m im
ln Φ m
eln Φm eim , e Φ m
Φ m Ae 1.192
im
To determine the constant A, by using normalization condition and angle of 𝜙 range
from 0 ≤ 𝜙 ≤ 2𝜋.
Φ Φ d Ae Ae d 1
2 2
im im
0 m m 0
Ae Ae d A
2 2 2
im im 2
eim eim d A2 e im im d 1
0 0 0
2
A2 e0 d 1, but e0 1
0
2 2
A2 d A2 0 1
0
47
2 A2 1
1
A2
2
1
A 1.193
2
Put Eq. (1.193) into Eq. (1.192), we obtain:
1
Φm 1.194
im
2
e
Since Φ𝑚 (𝜙) is periodic (cyclic) coordinate, we must have:
Φm Φm 2 or
1 im 2 1 im im
Φm e e , e cos m i sin m
2 2
cos m 2 i sin m 2
im 2
e
cos m cos 2 m sin m sin 2 m i sin m cos 2m i sin 2m cos m
1 0 1 0
cos m i sin m 1.195
im 2
e
For Φ𝑚 (𝜙) to be single value:
eim eim 2 eim eim 2
eim eim eim 2
eim 2 1, where m is an int eger m 0, 1, 2, 3,... 1.196
Substitute Eq. (1.194) into Eq. (1.190), we obtain:
1
Yl , m , Θl , m e 1.197
im
2
48
Eigen function of 𝑳̂𝟐
Let us focus on determining Eigen functions Θ𝑙,𝑚 (𝜃) of 𝐿̂2 :
From Eq. (1.185) and Eq. (1.188), we have:
1 1 2
Lˆ2Yl , m , 2
l l 1 Yl , m , , Lˆ2 Lˆ2 2
sin
sin 2 2
sin
1 1 2
2
sin Yl , m , 2
l l 1 Yl , m ,
sin 2 2
sin
1 1 2
sin Yl , m , l l 1 Yl , m ,
sin 2 2
sin
1 1 2
sin l,m
Y , Yl , m , l l 1 Yl , m , 1.198
sin sin 2 2
Put Eq. (1.190) into Eq. (1.198), we get:
1 1 2
sin Θ
l,m Φ Θl , m Φm l l 1 Θl , m Φm
sin sin 2 2
m
Φm Θl , m
2
sin Θl , m Φm l l 1 Θl , m Φm 1.199
sin sin
2 2
1
Multiply Eq. (1.199) by , we obtain:
Φ m
Φ m Θl , m 1
2
l l 1 Θl , m Φm
1
sin Θ Φ
sin sin Φm Φm
l,m 2 2 m
1 Θl , m 1 2
sin Θ Φm l l 1 Θl , m
sin sin Φm
l,m 2 2
1 d d Θl , m 1 d2
sin Θ l,m
Φm l l 1 Θl , m 1.200
sin d d sin Φm d
2 2
49
Again multiply Eq. (1.200) by sin2 𝜃, we obtain:
1 d d Θl , m 1 d2
sin 2 sin Θ Φm l l 1 sin 2 Θl , m
sin d d sin Φm d
l,m 2 2
sin 2 d sin Θl , m 1
2
d d2
sin Θ Φm l l 1 sin 2 Θl , m
sin d d sin Φ m d
l,m
2 2
d d 1 d2
sin sin Θl , m Θl , m Φm l l 1 sin 2 Θl , m 1.201
d d Φm d 2
1
Where Φm
im
2
e
From Eq. (1.201):
1 d2 1 d2 1
im
Φ 2 e
Φ m d 2 im d
2
m
1
2
e
2 e
im 1 d2
2
2 d
e im
1 im
2 e
2
im ime
im
i 2 m2 e
im im
e , i2 1
im im
m2 e
m2 e , 1
0 0
e
1 d2
Φ m m 2 1.202
Φ m d 2
Put Eq. (1.202) into Eq. (1.201), we obtain:
d d
sin sin Θl , m m2 Θl , m l l 1 sin 2 Θl , m
d d
d d
sin sin Θl , m l l 1 sin 2 Θl , m m2 Θl , m 0 1.203
d d
50
Evaluating the first term of Eq. (1.203), by product rule of differentiation :
d d d d2
sin sin Θ sin cos Θ sin Θl , m
d d d d
l,m l,m
2
d d d2 d
sin sin Θ sin 2
Θl , m sin cos Θl , m 1.204
d d d d
l,m
2
Put Eq. (1.204) into Eq. (1.203), we obtain:
d2 d
sin 2 Θl , m sin cos Θl , m l l 1 sin 2 Θl , m m2 Θl , m 0 1.205
d 2
d
We are going to change variable using as follows :
x cos 1.206
dx
sin 1.207
d
Now,
d d dx dx
Θl , m Θl , m x , but sin
d dx d d
d d
Θl , m Θl , m x sin
d dx
d d
Θl , m sin Θl , m x 1.208
d dx
And
d2 d d d d dx dx
Θl , m Θl , m Θl , m x , but sin
d 2
d d d dx d d
d2 d d
Θl , m sin Θl , m x
d 2
d dx
d d d
cos Θl , m x sin Θl , m x
dx d dx
d d dx d
cos Θl , m x sin Θl , m x
dx dx d dx
d d dx d dx
cos Θl , m x sin Θl , m x , but sin
dx d d dx d
d d d
cos Θl , m x sin sin Θl , m x
dx dx dx
d d d
cos Θl , m x sin 2 Θl , m x
dx dx dx
d2 d2 d
Θ sin 2
Θl , m x cos Θl , m x 1.209
d 2 l,m 2
dx dx
51
Substituting Eq. (1.209) and Eq. (1.208) into Eq. (1.205), we obtain:
d2 d d
sin 2 sin 2 2 Θl , m x cos Θl , m x sin cos sin Θl , m x l l 1 sin 2 Θl , m m2 Θl , m x 0
dx dx dx
d 2
d d
sin 2 sin 2 2 Θl , m x cos Θl , m x sin 2 cos Θl , m x l l 1 sin 2 Θl , m m2 Θl , m x 0 1.210
dx dx dx
Divided both side of Eq. (1.210) by sin2 𝜃:
sin 2 2 d 2 d sin 2 d sin 2 m2
sin 2 Θl , m x cos Θl , m x cos Θl , m x l l 1 2 Θl , m 2 Θl , m x 0
sin
2
dx dx sin
2
dx sin sin
2 2
d d d m
sin 2 2 Θl , m x cos Θl , m x cos Θl , m x l l 1 Θl , m 2 Θl , m x 0
dx dx dx sin
2 2
d d m
sin 2 2 Θl , m x 2cos Θl , m x l l 1 Θl , m x 2 Θl , m x 0
dx dx sin
d 2
d m 2
sin 2 2 Θl , m x 2cos Θl , m x l l 1 2 Θl , m x 0 1.211
dx dx sin
This equation is known as the Legendre differential equation.
Since,
x cos
sin 1 cos
2 2
1.212
sin 2 1 x 2
Therefore, put Eq. (1.212) into Eq. (1.211), we obtain:
d2 m2
1 x2 Θ x 2 x
d
Θ x l l 1 Θ x 0 1.213
dx 2
l,m
dx
l,m
1 x2 l , m
This is the associated Legendre equation, which is reduced to Legendre equation when
𝑚 = 0.
The associated Legendre equation is often written as:
m2
1 x2 Θl'', m x 2 xΘl'', m x l l 1 Θl , m 1 x2
Θl , m x 0 1.214
d2 d
Where Θl'', m x 2
Θl , m x and Θl'', m x Θl , m x .
dx dx
And,
Becomes the Legendre equation, when 𝑚 = 𝑜:
1 x Θ x 2xΘ x l l 1 Θ x 0
2 ''
l,m
''
l,m l,m 1.215
52
For integral value of 𝑚 and 𝑙, this equation has solution.
The Legendre Polynomials of degree of 𝑙 (angular quantum) is given by the formula:
1
l
dl
l
pl x l
1 x2 1.216
2 l ! dx
Where 𝑝𝑙 (𝑥) is the 𝑙 𝑡ℎ Legendre polynomial.
The associated Legendre functions are given by:
dm
pl , m x plm x 1 x2 pl x 1.217
m
dx m
The first six Legendre polynomials
1
0
d0
0
For l 0 , p0 x 1 x2 1 1.218
0
0
2 0! dx
1
1
For l 1 , p1 x
d
1 x2 0 2x
1 2x
1.219
1
1
x
2 1! dx 2 2
1
2
d2
2
For l 2 , p2 x 1 x2 1.220
2
2
2 2! dx
4 d
1 d2
8 dx 2
2 1 x 2 2 x
8 dx
1 x2 x
1 d
2 dx
x x3 1 3x 2
1
2
For l 2 , p2 x
1
2
3x 2 1 1.221
For l 3 , p3 x
1
2
5 x 3 3x 1.222
For l 4 , p4 x
1
8
35x 4 30 x 2 3 1.223
For l 5 , p5 x
1
2
63x5 70 xx3 15x 1.224
The first six Legendre polynomials
dm
pl , m x plm x 1 x2 pl x
m
dx m
d0
For l 0, m 0 , p00 x 1 x2 p0 x , p0 x 1
0
dx0
53
For l 0, m 0 , p00 x 1 1.225
d1
For l 1, m 1 , p11 x 1 x2 p1 x , p1 x x
1
dx1
1 x dxd x
2
For l 1, m 1 , p11 x 1 x
2
1.226
d0
For l 1, m 0 , p10 x 1 x
2 0
dx0
p1 x , p1 x x
For l 1, m 0 , p10 x x 1.227
For l 0, m 1 , p01 x 0 1.228
For l 2, m 2 , p22 x 3 1 x 2 1.229
For l 3, m 1 , p31 x
3
2
5 x 2 1 1 x
2
1.230
For l 3, m 2 , p32 x 15x 1 x 2 1.231
3
For l 3, m 3 , p x 15x 1 x
3
3
2 2
1.232
The solutions of polar angle, Θ𝑙,𝑚 (𝜃) in terms of the associated Legendre functions
𝑝𝑙𝑚 (cosθ) = 𝑝𝑙𝑚 (𝑥) → 𝑥 = 𝑐𝑜𝑠𝜃 , is given by:
Θl , m Cl , m plm cos 1.233
The constant 𝐶𝑙,𝑚 can be determined from orthonormalization condition.
2
l ', m ' m, l d d sin l ', m ' , , l , m l ', m m ', m
0 0
1.234
Which can be written as:
2
d d sin Yl ', m ' , Yl , m , l ', m m ', m 1.235
0 0
54
This relation is known as the normalization condition of spherical harmonics, and put Eq.
(1.197) into Eq. (1.235), we obtain:
2
2 Cl , m 2
d d sin Yl , m , d d sin plm cos 1 1.236
2 2
0 0 2 0 0
From the theory of associated Legendre function we have:
2 2 l m !
d d sin plm cos l ,l ' 1.237
0 0 2l 1 l m !
By comparing the normalization of spherical harmonics and the theory of associated
Legendre function, the constant 𝐶𝑙,𝑚 is given by:
2l 1 l m !
Cl , m 1 , m 0 1.238
m
2 l m !
Substituting Eq. (1.238) into Eq. (1.233), we obtain the eigen functions of 𝐿̂2 :
2l 1 l m ! m
Θl , m 1 pl cos 1.239
m
2 l m !
Finally, the eigen functions, 𝑌𝑙,𝑚 (𝜃, 𝜙) of 𝐿̂2 and 𝐿̂𝑧 can be obtained by substituting Eq.
(1.197) and Eq.(1.239) into Eq. (1.190):
2l 1 l m ! m 1
Yl , m , 1 pl cos
m im
e
2 l m ! 2
2l 1 l m ! m
Yl , m , 1 pl cos e , 1.240
im
mo
m
4 l m !
These are called the normalized spherical harmonics.
If 𝑚 < 0, the formula is:
55
2l 1 l m ! m
Yl , m , 1 pl cos e 1.241
m im
4 l m !
The first four spherical harmonics
2l 1 l m ! m
Yl , m , Yl m , 1 pl cos e
m im
4 l m !
2(0) 1 0 0 ! 0
For l 0, m 0 , Y00 , 1 p0 cos e , p0 cos p0 x 1
0 0
0 0
4 0 0 !
1 0!
0! 1
4 0!
1
For l 0, m 0 , Y00 , 1.242
4
2(1) 1 1 0 ! 0
For l 1, m 0 , Y10 , 1 p1 cos e , p1 cos p0 x x cos
0 0
0 0
4 1 0 !
3 1!
cos , 1! 1
4 1!
3
For l 0, m 0 , Y10 , cos 1.243
4
2(1) 1 1 1! 1
For l 1, m 1 , Y11 , 1 p1 cos e , p1 cos p1 x 1 x
1 i
1 1 2
4 1 1!
x cos ,1 x 2 1 cos 2 sin 2
1 x 2 1 cos 2 sin 2 sin
3 0! i
sin e , 0! 1, 2! 2
4 2!
3
For l 1, m 1 , Y11 , 1.244
i
sin e
8
Spherical harmonic in Cartesian coordinate
Note that 𝑌𝑙,𝑚 (𝜃, 𝜙) can also expressed in terms of the Cartesian coordinates.
56
x
x r sin cos , sin cos
r
y
y r sin sin , sin sin 1.245
r
z
z r cos , cos
r
x iy
sin cos i sin cos
r
sin cos i cos , cos i cos e
i
x iy
1.246
i
sin e
r
Substituting Eq. (1.245) and Eq. (1.246) into Eq. (1.243) and Eq. (1.244), we obtain:
3 3 z
Y10 , cos 1.247
4 4 r
3 3 x iy
Y11 , 1.248
i
sin e
8 8 r
Exercise
1. Find the expression of 𝑌30 (𝜃, 𝜙) in Cartesian coordinate.
1.7. Matrix representation of angular momentum operator
The representation of an operator is formed by considering its action on a given set of basis
vector
In basis that we label |𝑈𝑖 ⟩, the components of an operator 𝑇̂ are found by forming the
following inner (scalar) product.
57
1 if i i
Tˆij U i Tˆ U j ij 1.249
0 if i # j
Where 𝑇̂𝑖𝑗 is element at row 𝑖 and column 𝑗
Tˆ11 Tˆ12 Tˆ13
Tˆij Tˆ21 Tˆ22 Tˆ23
ˆ
T31 Tˆ32 Tˆ33
U Tˆ U U1 Tˆ U 2 U1 Tˆ U 3
1 1
Tˆij U 2 Tˆ U1 U 2 Tˆ U 2 U 2 Tˆ U 3 1.250
U 3 Tˆ U1 U 3 Tˆ U 2 U 3 Tˆ U 3
We now proceed to find matrix representations for the angular momentum operators.
We continued to work in the basis |𝑙, 𝑚⟩, which are the eigen states of 𝐿̂2 and 𝐿̂𝑧 .
Now the operators of 𝐿̂2 and 𝐿̂𝑧 are represented in the matrix form as:
Lˆ2 l , m 2
l l 1 l , m
l ', m ' Lˆ2 l , m 2
l l 1 l ', m ' l , m 2
l l 1 l 'l m ' m 1.251
Similarly,
Lˆz l , m m l , m
l ', m ' Lˆz l , m m l ', m ' l , m m l 'l m ' m 1.252
Example
A. Find the matrices representation of 𝐿̂2 , 𝐿̂𝑧 , 𝐿̂+ , 𝐿̂− , 𝐿̂𝑥 and 𝐿̂𝑦 in the state |𝑙, 𝑚⟩? (consider 𝑙 = 1)
Given
l , m , l 1, m 1,0, 1
Required
A) Lˆ2 ?, B) Lˆz ?,
C ) Lˆ ? D) Lˆ ?, E ) Lˆx ? F ) Lˆ y ?
58
Solution
A. since 𝑙 = 1, 𝑚 = 1, 0, −1, so that the eigen state of 𝐿̂2 becomes
l , m 1,1 , 1,0 , 1, 1 ket of of eigenstate
l ', m ' 1,1 , 1, o , 1, 1 bra of eigenstate
From the eigenvalue of 𝐿̂2 , we obtain the value of eigenvalue and Eigen ket of 𝐿̂2 as
follows:
Lˆ2 l , m l l 1 l , m , if l 1, m 1, 0, 1
2
Lˆ2 1,1 2 (1) 1 1 1,1
2 2 1,1
Lˆ2 1, 0 2 (1) 1 1 1, 0 eigenvalue and eigenket 1.253
2 2 1, 0
Lˆ2 1, 2 (1) 1 1 1, 1
2 1, 1
2
And
l ', m ' 1,1 , 1, o , 1, 1 bra of eigenstate 1.254
In the matrix form we can write as:
l ', m ' Lˆ2 l , m 2
l l 1 l ', m ' l , m 2 2 l 'l m ' m
Lˆ2 1,1
Lˆ2 1,1 1, o
1, 1 Lˆ2 1, 0
1.255
Lˆ2 1, 1
59
ˆ2
1,1 L 1,1 1,1 Lˆ 1, 0
2
1,1 Lˆ 1, 1
2
2 2 1,1 2 2
1,0 2 2 1, 1
1, o Lˆ2 1,1 1, o Lˆ2 1, 0 1, o Lˆ2 1, 1
2 2 1,1 2 2 1, 1
2
2 1,0
1, 1 Lˆ2 1,1 1, 1 Lˆ2 1, 0 1, 1 L 1, 1
ˆ2
2 2 1,1 2 2
1,0 2 2 1, 1
l ', m ' Lˆ2 l , m 2
l l 1 l ', m ' l , m 2 2 l 'l m ' m
Lˆ2 1,1
Lˆ2 1,1
1, o
1, 1 Lˆ2 1, 0
1.255
Lˆ2 1, 1
ˆ2
1,1 L 1,1 1,1 Lˆ2 1, 0 1,1 Lˆ2 1, 1
2 2 1,1 2 2
1,0 2 2 1, 1
1, o Lˆ2 1,1 1, o Lˆ 1, 0
2
1, o Lˆ2 1, 1
2 2 1,1 2 2 1, 1
2
2 1,0
1, 1 Lˆ2 1,1 1, 1 Lˆ 1, 02
1, 1 Lˆ 1, 1
2
2 2 1,1 2 2
1, 0 2 2 1, 1
1,1 2 2 1,1 1,1 2 2
1, 0 1,1 2 1, 1
2
1, o 2 2 1,1 1, o 2 2
1, 0 1, o 2 2 1, 1
1, 1 2 1,1
2
1, 1 2 2
1, 0 1, 1 2 2 1, 1
1,11,1 1,11, 0 1,11, 1
Lˆ2 2 2 1, o 1,1
1, o 1, 0 1, o 1, 1 1.256
1, 11,1 1, 11, 0 1, 11, 1
1 if l ' l and m ' m
l ', m ' Lˆ2 l , m 2
l l 1 l ', m ' l , m 2 2 l 'l m ' m
0 if l ' l and m ' m
60
1,11,1 2 2
2 2, 1,11,0 2 2
0, 1,11, 1 2 2
11 11 0
11 11 11 10
1 0 0
1, o 1,1 2 2
0,
11 01 1, o 1,0 2 2
2 2,
11 00 1, o 1, 1 2 2 11 0 1 0 1.257
0 1 0
1, 11,1 2 2
11 11 0, 1, 11,0 2 2
11 10 0, 1, 11, 1 2 2 11 11 2 2
0 0 1
Put Eq. (1.257) into Eq. (1.256) we obtain the matrix representation of 𝐿̂2 :
1 0 0
0 1 0
Lˆ2 2
2
1.258
0 0 1
B. From the eigenvalue and Eigen state of 𝐿̂𝑧 , we have:
Lˆz l , m m l , m , if l 1, m 1,0, 1
l , m 1,1 , 1,0 , 1, 1 ;
Lˆz 1,1 1,1
Lˆz 1, 0 0 eigenvalue and eigenket 1.259
Lˆz 1, 1 1, 1
And
l ', m ' 1,1 , 1, o , 1, 1 bra of eigenstate 1.260
l ', m ' Lˆz l , m m l ', m ' l , m m l 'l m ' m
Lˆz 1,1
Lˆz 1,1
1, o
1, 1 Lˆz 1, 0
Lˆz 1, 1
61
1,1 Lˆz 1,1 1,1 Lˆz 1, 0 1,1 Lˆz 1, 1
1, o Lˆz 1,1 1, o Lˆz 1, 0 1, o Lˆz 1, 1
1, 1 Lˆz 1,1 1, 1 Lˆz 1, 0 1, 1 Lz 1, 1
ˆ
1,1 1,1 1,1 0 1,1 1, 1
1, o 1,1 1, o 0 1, o 1, 1
1, 1 1,1 1, 1 0 1, 1 1, 1
1,11,1 0 1,11, 1
Lˆz 1, o 1,1
0 1, o 1, 1 1.261
1, 11,1 0 1, 11, 1
1,11,1 1111 , 1,11, 0 0 1110 0, 1,11, 1 1111 0
1 0
0
1, o 1,1 11 01 0, 1, o 1, 0 0 11 00 0(1) 0, 1, o 1, 1 11 01 0 1.262
0 1 0
1, 11,1 11 11 0, 1, 11, 0 0 11 10 0, 1, 11, 1 11 11
0 0 1
Put Eq. (1.262) into Eq. (1.261) we obtain the matrix representation of 𝐿̂𝑧 :
1 0 0
Lz 0 0 0
ˆ 1.263
0 0 1
C. Now let’s find matrix representations of ladder operators (raising or step-up operator). The
act on the states in the following way:
Lˆ l , m l l 1 m m 1 l , m 1 , if l 1, m 1,0, 1
62
Lˆ 1,1 11 1 11 1 1,1 1
2 2 1, 2
Lˆ 1,1 0
Lˆ 1,0 11 1 0 0 1 1,0 1
2 0 1,1 eigenvalue and eigenket 1.264
Lˆ 1,0 2 1,1
Lˆ 1, 1 11 1 1 1 1 1, 1 1
2 0 1,0
Lˆ 1, 1 2 1,0
And
l ', m ' 1,1 , 1, o , 1, 1 bra of eigenstate 1.265
Therefore, the matrix representation of step-up or raising operator is given as:
Lˆ
l l 1 m m 1 l ', m ' l , m 1 l l 1 m m 1 l 'l m ' m1
Lˆ 1,1
Lˆ 1,1 1, o
1, 1 Lˆ 1, 0
Lˆ 1, 1
ˆ
1,1 L 1,1 1,1 Lˆ 1, 0 ˆ
1,1 L 1, 1
0 2 1,1 2 1,0
1, o Lˆ 1,1 1, o Lˆ 1, 0 1, o Lˆ 1, 1
0 2 1,1 2 1,0
1, 1 Lˆ 1,1 1, 1 Lˆ 1, 0 1, 1 L 1, 1
ˆ
0 2 1,1 2 1,0
63
0 1,1 2 1,1 1,1 2 1, 0
0 1, o 2 1,1 1, o 2 1, 0
0 1, 1 2 1,1 1, 1 2 1, 0
0 1,11,1 1,11, 0
Lˆ 2 0
1, o 1,1 1, o 1, 0 1.266
0 1, 11,1 1, 11, 0
1,11,1 2 1111 2 1,11, 0 2 1110 0
1 0
1, o 1,1 2 11 01 0, 1, 0 1, 0 2 11 00 2 1.267
0 1
1, 11,1 2 11 11 0, 1, 11, 0 2 11 10 0
0 0
Put Eq. (1.267) into Eq. (1.266), we obtain the matrix representation of raising operator:
0 1 0
L 2 0 0 1
ˆ 1.268
0 0 0
D. Let’s find matrix representations of ladder operators (lowering or step-down operator). The
act on the states in the following way:
Lˆ l , m l l 1 m m 1 l , m 1 , if l 1, m 1,0, 1
Lˆ 1,1 11 1 11 1 1,1 1
2 0 1,0
ˆ
L 1,1 2 1,0
Lˆ 1,0 11 1 0 0 1 1,0 1
2 0 1, 1 eigenvalue and eigenket 1.269
Lˆ 1, 0 2 1, 1
Lˆ 1, 1 11 1 1 1 1 1, 1 1
2 2 1, 2
Lˆ 1, 1 0
l ', m ' 1,1 , 1, o , 1, 1 bra of eigenstate 1.270
64
The matrix representation(inner) product of lowering operator 𝐿̂− is given by
Lˆ
l l 1 m m 1 l ', m ' l , m 1 l l 1 m m 1 l 'l m ' m1
Lˆ 1,1
Lˆ 1,1 1, o
1, 1 Lˆ 1, 0
Lˆ 1, 1
ˆ
1,1 L 1,1 1,1 Lˆ 1, 0 1,1 Lˆ 1, 1
2 1,0 2 1, 1 0
1, o Lˆ 1,1 1, o Lˆ 1, 0 1, o Lˆ 1, 1
2 1,0 2 1, 1 0
1, 1 Lˆ 1,1 1, 1 Lˆ 1, 0 1, 1 Lˆ 1, 1
2 1,0 2 1, 1 0
1,1 2 1, 0 1,1 2 1, 1 0
1, o 2 1, 0 1, o 2 1, 1 0
1, 1 2 1, 0 1, 1 2 1, 1 0
1,11, 0 1,11, 1 0
Lˆ 2 1, o 1, 0
1, o 1, 1 0 1.271
1, 11, 0 1, 11, 1 0
1,11, 0 2 1110 0, 1,11, 1 2 1111 0
0 0
1, o 1, 0 2 11 00 2 , 1, 0 1, 1 2 11 01 0 1.272
1 0
1, 11, 0 2 11 10 0, 1, 11, 1 2 11 11 2
0 1
Put Eq. (1.272) into Eq. (1.271), we obtain the matrix representation of lowering operator:
0 0 0
L 2 1 0 0
ˆ 1.273
0 1 0
65
E. To find the matrix representation of 𝐿̂𝑥 , by considering ladder operator property as follow:
Lˆ Lˆ Lˆx iLˆ y Lˆx iLˆ y
Lˆ Lˆ 2Lˆ x
1
2
1
2
1
Lˆx Lˆ Lˆ Lˆ Lˆ
2
1 1
Lˆx Lˆ Lˆ
2 2
0 1 0 0 0 0
2 2
0 0 1 1 0 0
2 2 0 1 0
0 0 0
0 0 1 0 0 0
2
0 1 0 0 1 0
2
0 0 0 1 0 0
0 1 0
2 1 0 1
Lˆx
1.274
2
0 1 0
F. To find the matrix representation of 𝐿̂𝑦 , again by considering ladder operator property as
follow:
Lˆ Lˆ Lˆx i Lˆ y Lˆx i Lˆ y
Lˆx i Lˆ y Lˆx i Lˆ y
Lˆ Lˆ 2iLˆ y
Lˆ y
1 ˆ
2i
1
1
L Lˆ Lˆ Lˆ
2i 2i
1 1
Lˆ y Lˆ Lˆ
2i 2i
66
0 1 0 0 0 0
2 2
0 0 1 1 0 0
2i 2i 0 1 0
0 0 0
0 0 1 0 0 0
2
0 1 0 0 1 0
2i
0 0 0 1 0 0
0 1 0
ˆ 2 1
Ly 1 0 1 , but i
2i i
0 1 0
0 1 0
i 2
1 0 1
2 0 1 0
i 0 i 1 i 0
2
i 1 i 0 i 1
2
i 0 i 1 i 0
0 i 0
2
Lˆ y
i 0 i 1.275
2
0 i 0
1.8. Spin, spin operator, pauli’s spin matrices
Spin is an intrinsic (internal) property of particles that is a similar to a types of angular
momentum.
The electron or microscopic particles are intrinsic or internal rotation or spinning motion
about its axis.
Spin is an intrinsic angular momentum.
Spin angular momentum operator ( ̂
𝑺)
The theory of spin is identical to the general theory of the angular momentum.
By analogy with vector angular momentum 𝐿̂ , spin is also represented by 𝑆̂ whose components
are 𝑆̂𝑥 , 𝑆̂𝑦 , 𝑆̂𝑧 and obey the same commutation relation as 𝐿̂𝑥 , 𝐿̂𝑦 , 𝐿̂𝑧 .
67
Sˆx , Sˆ y i Sˆz
Sˆz , Sˆx i Sˆ y
1.276
Sˆ y , Sˆz i Sˆx
As we represented in angular momentum, the total spin 𝑆̂ 2 are commutes with 𝑆̂𝑧 ;
Sˆ 2 , Sˆz Sˆ 2 , Sˆx Sˆ 2 , Sˆ y 0
1.277
We can labeling the eigenstate of spin operators 𝑆 by |𝑠, 𝑚𝑠 ⟩
Hence, 𝑆̂ 2 and 𝑆̂𝑧 commutes, they have common eigenstate:
Sˆ 2 s, ms 2
s s 1 s, ms 1.278
And
Sˆz s, ms ms s 1 s, ms 1.279
Where 𝑚𝑠 = −𝑠, −𝑠 + 1, … 𝑠 − 1, 𝑠
And also, the raising and lowering operator is given by:
Sˆ s, ms s s 1 ms ms 1 s, ms 1 1.280
Sˆ s, ms s s 1 ms ms 1 s, ms 1 1.281
Where
Sˆ Sˆx iSˆ y 1.282
Sˆ Sˆx iSˆ y 1.283
The spin states forms an orthonormal and complete basis as follow:
1 for s s ' & ms ms'
s ', m s, ms s ' s m' m
'
1.284
0 for s s ' & ms ms
s '
s
s
s, m
ms
s s, ms Iˆ, 1.285
Where 𝐼̂ is the unit matrix.
68
In nature, every fundamental (elementary) particles has a specific spin.
Some particles have integer spins 𝑠 = 0, 1, 2,⋅⋅⋅
Example
Pi mesons have spin 𝑠 = 1
Photon have spin 𝑠 = 1
1 3 5
Some particle have half-odd-integers spin 𝑠 = 2 , 2 , 2 ,⋅⋅⋅
Example
1
The electron, protons, and neutrons have spin 𝑠 = 2.
3
The deltas have spin 𝑠 = 2.
Particles having half-odd-integers spin are called Fermions (quark, electrons, protons,
neutrons etc.)
Particles having integer spin are called Bosons (pions, photons, Gravitons, Gluon, 𝑊 ±,
𝑍 𝑜 bosons etc.)
𝟏
Spin and the pauli matrices
𝟐
A measurement of the spin of an electron or any spin- ½ particle can have only two possible
results:
Spin up and
Spin down
1
In spin − 2 particles:
ℏ
o There are only two possible results of a measurement; these are ± 2.
o States are represented by column vectors with two components.
o Operators are represented by 2 × 2 matrices.
1 1
For a particle with spin 2, the quantum number 𝑚𝑠 takes two value: 𝑚𝑠 = 2 and
1
𝑚𝑠 − 2.
The particle can be in either of two states:
1 1
|𝑠, 𝑚𝑠 ⟩ = | , ⟩ Called spin up state (1.286)
2 2
69
1 1
|𝑠, 𝑚𝑠 ⟩ = | , − ⟩ Called spin down state (1.287)
2 2
We now proceed to obtain matrix representation for spin up and spin down eigenstate:
1 1
, 1.288
2 2
1 1
, 1.289
2 2
The matrix representation for a vector |𝜓⟩ in the |𝛼⟩ and |𝛽⟩ basis is:
1.290
We note that:
1 1 1 1
2,2 2,2
1
0 1.291
1 1 1 1
, ,
2 2 2 2
1 1 1 1
2 , 2 2 , 2
0
1 1.292
1 1 1 1
, ,
2 2 2 2
Therefore:
1 1 1
, Spin upstate 1.293
2 2 0
1 1 0
, Spin down state 1.294
2 2 1
The eigenvalues of 𝑆̂ 2 and 𝑆̂𝑧 are given by:
1 1 1
Sˆz s, ms ms s, ms , s , ms and ms
2 2 2
1 1 1 1
Sˆz , ,
2 2 2 2 2
eigen value and eigenstate 1.295
1 1 1 1
Sˆz , ,
2 2 2 2 2
70
And
1 1 1
Sˆ 2 s, ms 2
s s 1 s, ms , s , ms and ms
2 2 2
1 1 11 1 1
Sˆ 2 , 2
1 ,
2 2 22 2 2
13 1 1
2
,
22 2 2
1 1 3 1 1
Sˆ 2 , 2
,
2 2 4 2 2
1.296
1 1 3 1 1
Sˆ 2 , 2
,
2 2 4 2 2
Example
1. Find the matrices representation and pauli matrices of 𝑆̂ 2 , 𝑆̂𝑧 , 𝑆̂+ , 𝑆̂− , 𝑆̂𝑥 𝑎𝑛𝑑 𝑆̂𝑦 in the state
1
|𝑠, 𝑚𝑠 ⟩ for 𝑆 = 2.
Given Required
1 1 1
for s , ms and ms A) Sˆ 2 & 2 ?
2 2 2
1 1 1 1
s, ms , , , B) Sˆz & z ?
2 2 2 2
S 2 s, ms C ) Sˆ & ?
Sˆz s, ms D) Sˆ & ?
Sˆ s, ms E ) Sˆx & x ?
Sˆ s, ms F ) Sˆ y & y ?
Sˆx s, ms
Sˆx s, ms
71
Solution
A. From the eigenstate of 𝑆̂ 2 we have:
1 1 1
Sˆ 2 s, ms 2
s s 1 s, ms , s , ms and ms
2 2 2
1 1 11 1 1
Sˆ 2 , 2
1 ,
2 2 22 2 2
13 1 1
2
,
22 2 2
1 1 3 1 1
Sˆ 2 , 2
,
2 2 4 2 2
eigenvalue and eigenstate of Sˆ
2
1.297
1 1 3 1 1
Sˆ 2 , 2
,
2 2 4 2 2
And
1
The bra of the eigenstate for 𝑠 = 2, is given by:
1 1 1 1
s ', ms' , , , 1.298
2 2 2 2
In the matrix form we can written as:
3 2
s ', ms' sˆ2 s, ms 2
s s 1 s ', ms' s, ms s ' s m' m
4 s s
2 1 1
sˆ ,
1 1 1 1 2 2
sˆ 2 , ,
2 2 2 2 2 1 1
sˆ ,
2 2
1 1 2 1 1 1 1 2 1 1
, sˆ , , sˆ ,
2 2 2 2 2 2 2 2
sˆ
2
1 1 1 1 1 1 2 1 1
, sˆ 2 , , sˆ ,
2 2 2 2 2 2 2 2
72
1 1 3 1 1 1 1 3 1 1
, 2
, , ,
2
2 2 4 2 2 2 2 4 2 2
1 1 3 1 1 1 1 3 2 1 1
, 2
, , ,
2 2 4 2 2 2 2 4 2 2
1 1 1 1 1 1 1 1
, , , ,
3 2 2 2 2 2 2 2 2 2
sˆ
2
1.299
4 1 1 1 1 1 1 1 1
, , , ,
2 2 2 2 2 2 2 2
From the inner (scalar) product property, we can write Eq. (1.299) as:
1 1 1 1 3 3 1 1 1 1 3
, , 2
1 1 1 1 2
, , , 2
1 1 1 1 0
2 2 2 2 4 4 2 2 2 2 4
22 22 22 2 2
1.300
1 0
1 1 1 1 3 1 1 1 1 3 3 2
, , 2
1 1 0, , , 2
1 1
4
11 1 1
2 2 2 2 4 2 2 2 2 4
22 22 22 2 2
1 1
Put Eq. (1.300) into Eq. (1.299), we obtain the matrix representation of 𝑆̂ 2 :
3 1 0
sˆ2 2
1.300
4 0 1
Hence we can write Eq. (1.300) in terms of pauli matrices:
1 0
2 x2 y2 z2 1 Iˆ 1.301
0 1
Therefore, the pauli matrices representation of Eq.(1.300) is:
3 1 0 3 2 2
sˆ2 2
0 1 4 1.302
4
B. From eigenstate of 𝑆̂𝑧 we have:
1 1 1
Sˆz s, ms ms s, ms , s , ms and ms
2 2 2
73
1 1 1 1
Sˆz , ,
2 2 2 2 2
eigen value and eigenstate 1.303
1 1 1 1
Sˆz , ,
2 2 2 2 2
And
1 1 1 1
s ', ms' , , , bra of eigenstate 1.304
2 2 2 2
The matrix representation of 𝑆̂𝑧 is given:
s ', ms' sˆ2 s, ms ms s ', ms' s, ms s ' s m' m
2 s s
1 1
sˆz ,
1 1 1 1 2 2
sˆz , ,
2 2 2 2 1 1
sˆz ,
2 2
1 1 1 1 1 1 1 1
, sˆz , , sˆz ,
2 2 2 2 2 2 2 2
1 1 1 1 1 1 1 1
, sˆz , , sˆz ,
2 2 2 2 2 2 2 2
1 1 1 1 1 1 1 1
, , , ,
2 2 2 2 2 2 2 2 2 2
sˆ
2
1 1 1 1 1 1 1 1
, , , ,
2 2 2 2 2 2 2 2 2 2
1 1 1 1
1 1 1 1
, , , ,
2 2 2 2 2 2 2 2
sˆ 2 1.305
2 1 1 1 1 1 1 1 1
, , , ,
2 2 2 2 2 2 2 2
74
From the inner (scalar) product property, we can write Eq. (1.299) as:
1 1 1 1 1 1 1 1
, , 1 1 1 1 , , , 1 1 1 1 0
2 2 2 2 2 22 22 2 2 2 2 2 2 2 2 22
1.306
1 0
1 1 1 1 1 1 1 1
, , 1 1 1 1 0, , , 1 1 1 1
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 22 2
1 1
Put Eq. (1.306) into Eq. (1.305), we obtain:
1 0
sˆ2 1.307
2 0 1
1 0
Where z pauli matrices
0 1
Therefore, matrix representation of 𝑆̂𝑧 in pauli matrices is given by:
1 0
sˆ2 z 1.308
2 0 1 2
C. Now let’s find matrix representations of ladder operators (raising or step-up spin operator)
1 1 1
S s, ms s s 1 ms ms 1 s, ms 1 , if s , ms , and ms
2 2 2
1 1 11 11 1 1
S , 1 1 , 1
2 2 22 22 2 2
13 13 1 3
,
22 22 2 2
3 3 1 3
,
4 4 2 2
1 1
S , 0 1.309
2 2
1 1 11 1 1 1 1
S , 1 1 , 1
2 2 22 2 2 2 2
3 11 1 1
,
4 22 2 2
75
3 1 1 1
,
4 4 2 2
4 1 1
,
4 2 2
1 1 1 1
S , , 1.310
2 2 2 2
And
1
The bra of eigenstate for 𝑆 = 2, is given by
1 1 1 1
s ', ms' , , , bra of eigenstate 1.311
2 2 2 2
The matrix representation of raising spin operator is also written as:
s ', ms' sˆ s, ms s s 1 ms ms 1 s ', ms' s, ms 1 s s 1 ms ms 1 s ' s m' m 1
s s
1 1
sˆ ,
1 1 1 1 2 2
sˆ , ,
2 2 2 2 1 1
sˆ ,
2 2
1 1 ˆ 1 1 1 1 ˆ 1 1
, S , , S ,
2 2 2 2 2 2 2 2
1 1 ˆ 1 1 1 1 ˆ 1 1
, S , , S , 0 1 1
ˆ 2 2 2 2 2 2 2 2 ,
S
2 2
1 1
1 1 1 1 ˆ 1 1 1 1 ˆ 1 1 1 1 ˆ 1 1
, Sˆ , , S , , S , , S ,
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
0 1 1
,
2 2
1 1 1 1 1 1 1 1
0 , , 0 , ,
2 2 2 2 2 2 2 2
S
ˆ 1.312
1 1 1 1 1 1 1 1
0 , , 0 , ,
2 2 2 2 2 2 2 2
76
From the inner (scalar) product property, we can write Eq. (1.299) as:
1 1 1 1 1 1 1 1
, , 1 1 1 1 , , , 1 1 1 1 0
1.313
2 2 2 2 22 22 2 2 2 2 22 22
1 1
Put Eq. (1.313) into Eq. (1.312), we obtain:
0 1
Sˆ
1.314
0 0
0 1
Where
0 0
0 1
Sˆ
1.315
0 0
D. Now let’s find matrix representations of ladder operators (lowering or step-down spin
operator)
1 1 1
S s, ms s s 1 ms ms 1 s, ms 1 , if s , ms , and ms
2 2 2
1 1 11 11 1 1
S , 1 1 , 1
2 2 22 22 2 2
13 1 1 1 1
,
22 2 2 2 2
3 1 1 1
,
4 4 2 2
4 1 1
,
4 2 2
1 1 1 1
S , , 1.316
2 2 2 2
1 1 11 1 1 1 1
S , 1 1 , 1
2 2 22 2 2 2 2
3 1 3 1 3
,
4 2 2 2 2
3 3 1 3
,
4 4 2 2
1 1
S , 0 1.317
2 2
77
And
1
The bra of eigenstate for 𝑆 = 2, is given by
1 1 1 1
s ', ms' , , , bra of eigenstate 1.318
2 2 2 2
The matrix representation of lowering spin operator is also written as:
s ', ms' sˆ s, ms s s 1 ms ms 1 s ', ms' s, ms 1
s s 1 ms ms 1 s ' s m' m 1
s s
1 1
sˆ ,
1 1 1 1 2 2
sˆ , ,
2 2 2 2 1 1
sˆ ,
2 2
1 1 ˆ 1 1 1 1 ˆ 1 1
, S , , S ,
2 2 2 2 2 2 2 2
1 1 ˆ 1 1 1 1 ˆ 1 1
, S , , S , 1 1
,
0
2 2 2 2 2 2 2 2
Sˆ
2 2
1 1 ˆ 1 1 1 1 ˆ 1 1 1 1 ˆ 1 1 1 1 ˆ 1 1
, S , , S , , S , , S ,
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
1 1 0
,
2 2
1 1 1 1 1 1 1 1
, , 0 , , 0
2 2 2 2 2 2 2 2
S
ˆ 1.319
1 1 1 1 1 1 1 1
, , 0 , , 0
2 2 2 2 2 2 2 2
From the inner (scalar) product property, we can write Eq. (1.319) as:
1 1 1 1 1 1 1 1
, , 1 1 1 1 0,
, , 1 1 1 1
1.320
2 2 2 2 22 2 2 2 2 2 2 22 2 2
0 1
Put Eq. (1.320) into Eq. (1.319), we obtain:
0 0
Sˆ
1.321
1 0
0 0
Where
1 0
0 0
Sˆ
1.322
1 0
78
E. To find the matrix representation of 𝑆̂𝑥 , by considering ladder operator property as follow:
Sˆ Sˆ Sˆx iSˆ y Sˆx iSˆ y
Sˆ Sˆ 2Sˆ x
1
2
1
2
1
Sˆx Sˆ Sˆ Sˆ Sˆ
2
Sˆx 1 Sˆ 1 Sˆ
2 2
0 1 0 0
2 0 0 2 1 0
0 0 1 0
2 0 1 0 0
0 1
Sˆx
2 1 0 1.323
0 1
Where x Pauli matrices
1 0
0 1
Sˆx
2 1 0 2 x 1.324
F. To find the matrix representation of 𝑆̂𝑦 , again by considering ladder operator property as
follow:
Sˆ Sˆ Sˆx iSˆ y Sˆx iSˆ y
Sˆ Sˆ 2iSˆ y
Sˆ y
2i
1 ˆ 1
1
S Sˆ Sˆ Sˆ
2i 2
Sˆ y 1 Sˆ 1 Sˆ
2i 2i
0 1 0 0 0 0 1 0 0 1 1
, i
2i 0 0 2i 1 0 2i 0 1 0 0 2i 1 0 i
0 i
Sˆ y
2 i 0 2 y 1.325
79
Pauli matrices
1
When 𝑆 = 2 , it convenient to introduced the Pauli matrices 𝜎𝑥 , 𝜎𝑦 , 𝜎𝑧 which are related to the
spin vector as follows
ˆ
S i 1.326
2
Where
0 1 0 i 1 0
x , y z 1.327
0
,
1 0 i 0 1
These are called Pauli matrices.
The square of any Pauli matrix gives the identity matrix.
x2 y2 z2 I 1.328
The ladder operator(Pauli matrix) is given by:
1
2
x i y
1.329
x i y
1
2
Example
1. Find the commutation of :
A) x , y ?
B ) z , x ?
C ) y , z ?
D ) , ?
E ) z , ?
80
Solution
A) x , y x y y x
0 1 0 i 0 i 0 1
1 0 i 0 i 0 1 0
0 0 1 i 0 i 1 0 0 0 i 1 0 1 i 0
1 0 0 i 1 i 0 0 i 0 0 1 i 1 0 0
i 0 i 0 i 0 i 0 i i 0 0
0 i 0 i 0 i 0 i 0 0 i i
2i 0 1 0 1 0
2i , but z
0 2i 0 1 0 1
x , y 2i z
B) z , x z x x z
1 0 0 1 0 1 1 0 0 1 0 1
0 1 1 0 1 0 0 1 1 0 1 0
0 1 0 1 0 2 0 1 i
2 , 1
1 0 1 0 2 0 1 0 i
2i 0 1 2 0 i 1
, i
i 1 0 i i 0 i
0 i 0 i 0 i
2i 2i , but y
i 0 i 0 i 0
z , x 2i y
81
C ) y , z y z z y
0 i 1 0 1 0 0 i
i 0 0 1 0 1 i 0
0 i 0 i 0 i 0 i 0 2i
i 0 i 0 i 0 i 0 2i 0
0 1 0 1
2i , but x
1 0 1 0
y , z 2i x
D) ,
0 1 0 0 0 0 0 1 1 0 0 0
0 0 1 0 1 0 0 0 0 0 0 1
1 0 0 0 1 0 1 0
, z
0 0 0 1 0 1 0 1
, z
E )i z , z z
1 0 0 1 0 1 1 0 0 1 0 1
0 1 0 0 0 0 0 1 0 0 0 0
0 1 0 1 0 2 0 1 0 1
2 , but
0 0 0 0 0 0 0 0 0 0
z , 2
ii ) z , z z
1 0 0 0 0 0 1 0 0 0 0 0
0 1 1 0 1 0 0 1 1 0 1 0
0 0 0 0 0 0 0 0 0 0
2 , but
1 0 1 0 2 0 1 0 1 0
z , 2
82
CHAPTER TWO
2. THE HYDROGEN ATOM
The hydrogen atom consists of an electron orbiting a proton, bound together by the
Coulomb force. While the correct dynamics would involve both particles orbiting about a
center of mass position, the mass differential is such that it is a very good approximation
to treat the proton as fixed at the origin.
Hydrogen atom is a system of two particles, a proton and a single electron, bounded by
e2
electrostatic force of attraction this is F , corresponding to the potential
4 o r 2
e2
V (r ) .
4 o r
The wave function then depends on six coordinates 𝑟𝑒 (𝑥𝑒 , 𝑦𝑒 , 𝑧𝑒 ) and 𝑟𝑝 (𝑥𝑝 , 𝑦𝑝 , 𝑧𝑝 ), where
𝑟𝑒 and 𝑟𝑝 are the electron and proton position vectors respectively.
According to the probabilistic interpretation of the wave function, the quantity
re , rp , t d 3 re d 3 rp represents the probability that a simultaneous measurement of the
2
electron and proton positions at time t will result in the electron being in the volume
element 𝑑 3 𝑟𝑒 and the proton 𝑑 3 𝑟𝑝 .
The time independent Schrödinger wav function for two particles of masses 𝑚𝑝 and 𝑚𝑒
in six rectangular coordinate representation is given by:
83
2
2 2 2 2
2 2 2
2 2 2 2 2 2
i
t
x p , y p , z p ,; xe , ye , ze , t 2m p x p y p z p 2me xe ye ze
2.1
V x p , y p , z p ,; xe , ye , ze , t x p , y p , z p ,; xe , ye , ze , t
2 2
2p e2 V r re , rp i re , rp E re , rp 2.2
2m p 2me t
Where ∇2𝑝 and ∇2𝑒 are laplacians which respect to proton and electron which depends only the
distance that separates electron and proton
r re rp 2.3
Potential energy 𝑉(𝑟) is given by the coulomb potential
e2
V (r ) 2.4
4 o r
Since V does not depend on time, the solutions of time independent Schrödinger Equation,
(Eq. 2.2) is given by :
re , rp , t re , rp , t e
iEt
2.5
Substitute Eq. (2.5) into Eq. (2.2) we obtain:
2 2
e2 V r re , rp , t e E re , rp , t e
iEt iEt
p
2
2m p 2me
2 2
p
2
e2 V r re , rp , t E re , rp , t 2.6
2m p 2me
84
2.1. Reduction to one body problems
In Classical mechanics (and Quantum), problems involving several particles, it is
convenient to separate the motion of the center of mass from relative motion of the
particles.
This allows the separation of the motion of the group of particles as a whole (the center of
mass motion) from internal motions that can involves mutual potential energies between
the particles.
Figure 2.1: A system of two particle, a proton and electron.
Two particles mass at 𝑅⃗𝑒 and 𝑅⃗𝑝 from the origin.
𝑟 = 𝑅⃗𝑒 − 𝑅⃗𝑝 is the separation between the two masses.
The interaction potential energy is a function of V(r).
𝑅⃗𝑐𝑚 = 𝑅⃗ is the center of mass.
𝑟𝑒 , and 𝑟𝑝 are the coordinates of masses relative to 𝑅⃗𝑐𝑚
From Figure 2.1: we have the general formula as follow:
The radius of center of mass of electron 𝑅⃗𝑒 is given by
Re Rcm re 2.7
re Re Rcm 2.8
85
The radius of center of mass of proton 𝑅⃗𝑝 is given by
Rp Rcm rp 2.9
rp Rp Rcm 2.10
The separation distance 𝑟 between the two mass (𝑚𝑒 𝑎𝑛𝑑 𝑚𝑝 )is:
r Re Rp 2.11
The center of mass is defined as:
me Re m p Rp
R Rcm position of center-of-mass 2.12
me m p
The position of individual particles (𝑟𝑒 and 𝑟𝑝 ) relative to the center of mass ( 𝑅⃗ ), can be
obtained as:
me Re m p R p
re Re Rcm , but R Rcm
me m p
me Re m p R p
re Re
Re me m p me Re m p R p
me m p me m p
me Re m p Re me Re m p R p
me m p
m p Re m p R p
me m p
m p Re R p , but R R r
me m p
e p
mp
re r 2.13
me m p
86
Similarly, relative position of proton from a center of mass is given by:
me Re m p R p
rp R p Rcm but R Rcm
me m p
me Re m p R p
Rp
R p me m p me Re m p R p
me m p me m p
me R p m p R p me Re m p R p
me m p
me R p me Re
me m p
me R p Re , but R Rp r
me m p
p
me
rp r 2.14
me m p
The total energy of two particles (electron and proton) is given by
E Te Tp V (r )
1 1 d d
E me Re' m p Rp' V (r ), where Re' Re and R p' R p 2.15
2 2
2 2 dt dt
Put the time derivative of Eq. (2.7) and Eq. (2.9) into Eq. (2.15) we obtain:
1
1
2.16
2 2
E me R ' re ' m p R ' rp ' V (r ) where Re' R ' re ',
2 2
Rp' R ' re '
Put the time derivative of relative position of electron Eq. (2.13) and proton Eq. (2.14) into
Eq. (2.16), we obtain:
87
2 2
1 mp 1 me mp me
E me R ' r ' m p R ' r ' V (r ), re ' r ', rp ' r'
2
me m p 2 me m p me m p me m p
m 2p r '2 2m p R ' r ' 1 2 2 '2
1
me R '2 m R ' me r
2me R ' r '
V (r )
2 me m p 2 me m p
2 p 2
me m p me m p
2 '2 2 '2
1 1 me m p r 1 2 me m p R ' r ' 1 1 m p me r 1 2 m p me R ' r '
me R '2 m R '2
V (r )
2 m m me m p 2 m m me m p
2 p 2
2 2 2 2
e p e p
2 '2 2 '2
1 1 me m p r me m p R ' r ' 1 1 m p me r m p me R ' r '
me R '
2
mp R '
2
V (r )
2 2 m m 2
me m p 2 2 m m 2
me m p
e p e p
2 '2 2 '2
1 1 me m p r 1 1 m p me r
me R '
2
mp R '
2
V (r )
2 2 m m 2 2 2 m m 2
e p e p
2 '2 2 '2
1 1 1 me m p r 1 m p me r
me R ' m p R '
2 2
V (r )
2 2 2 m m 2 2 m m 2
e p e p
1 me m p me m p '2
1
2
me m p R '2
2 m m 2
r
e p
1 me m p me m p
me m p R ' '2
1 2
r V (r )
2 2 me m p me m p
1 me m p
1
2
me m p R '2 r '2 V (r )
2 me m p
2.17
Hence, from Eq. (2.17), we have:
𝑚𝑒 + 𝑚𝑝 = 𝑀 is called total mass (2.18)
And
𝑚𝑒 𝑚𝑝
= 𝜇 is known as reduced mass (2.19)
𝑚𝑒 + 𝑚𝑝
Put Eq. (2.18) and Eq. (2.19) into Eq. (2.17), we obtain:
1 1
E MR '2 r '2 V (r ) 2.20
2 2
88
From Eq. (2.20), the time derivative,
𝑑
𝑅⃗ ′ = 𝑅⃗ = 𝑉
⃗𝑅 (2.21)
𝑑𝑡
Is known as the center of masses velocity located at coordinate of center of mass 𝑅⃗ .
The coordinate of the center of mass is given by 𝑅⃗ = 𝑋𝑖̂ + 𝑌𝑗̂ + 𝑍𝑘̂.
Again from Eq. (2.20), the time derivative of relative coordinate is given by:
𝑑
⃗𝑟
𝑟 ′ = 𝑑𝑡 𝑟 = 𝑉 (2.22)
Is known as the relative velocity of particles which at located at coordinate 𝑟
The relative coordinate of the electron with respect to proton is 𝑟 = 𝑥𝑖̂ + 𝑦𝑗̂ + 𝑧𝑘̂.
Put Eq. (2.21) and Eq. (2.22) into Eq. (2.20), we obtain the total Energy of a particles:
1 1
E MVR2 Vr2 V (r ) 2.23
2 2
From Eq. (2.23) we conclude that there is a partition of total Energy in terms of the center of
mass Energy and the relative Energy.
1 1
E MVR2 Vr2 V (r ) 2.24
2 2
Ecm Erel
E Ecm Erel 2.25
The total Energy in terms of the momentum which is associated with a coordinate of center
of mass and relative coordinate is given by as flows:
PR MVR ,
PR
VR 2.26
M
89
Pr Vr ,
Pr
Vr 2.27
Substituting Eq. (2.26) and Eq. (2.27) into Eq. (2.23), we obtain Energy in the form of
momentum representation:
1 P 1 P
2
E M R r V (r )
2 M 2
1 P2 1 Pr2
M R2 2 V (r )
2 M 2
PR2 PR2
E V (r ) 2.28
2M 2
Total Energy can be expressed in terms of Hamiltonian operators as follow:
Hˆ Eˆ
Pˆ 2 Pˆ 2
Hˆ R R V (r ) 2.29
2M 2
We know that the linear operator can be expressed in terms of configuration space is given
by:
PR i R
PR2 i R i 2 2 2R , but i 2 1
2
PR2 2 2R 2.30
And
Pr i r
Pr2 i r i 2 2 2r , but i 2 1
2
Pr2 2 r2 2.31
Substituting Eq. (2.30) and Eq. (2.31) into Eq. (2.29), we obtain:
2 2
Hˆ 2R r2 V (r ) 2.32
2M 2
90
Eq. (2.32) shows the partition of Hamiltonian in terms of the center of masses of Hamiltonian
and the relative Hamiltonian.
2
2 2
Hˆ 2R r V (r ) 2.33
2M 2
Hˆ cm Hˆ rel
Hˆ Hˆ cm Hˆ rel 2.34
We convert the total Hamiltonian (Eq. (2.32) into the time –independent Schrödinger
equations (Eq. (2.6) as:
Hˆ E R, r E E R, r 2.35
2 2
2M R 2 r V (r ) E R, r E E R, r
2 2
2.36
Where
2 2 2
2
X 2 Y 2 X 2
R
2.37
2 2 2
r 2 2 2
2
x y z
And
E R, r re , rp 2.38
2.2. Separation of Variables (Separation of the Center of Mass Motion),
Spherical eigen function
Since Eq. (2.36) is the combination of Center of mass and relative motion, we decompose or
separate such types of Equations by the help of variable method:
Let us assume that:
E R, r Φ( R) r 2.39
91
Where Φ( R) and r are the wave functions of center of mass and relative motion
respectively.
Put Eq. (2.39) into Eq. (2.36), we obtain:
2 2
2M R 2 r V (r ) Φ( R) r EΦ( R) r
2 2
2 2
Φ( R) r
2
r2 r Φ( R) V (r )Φ( R) r EΦ( R) r 2.40
2
R
2M
Divided both side of Eq. (2.40) by Φ( R) r
2 2
1 1
2R Φ( R) 2r r V (r ) E
2M Φ( R) 2 r
ER Er
2
1 2 1
2
Φ( R ) 2r r V (r ) E 2.41
2 r
R
2M Φ( R)
The first bracket depends on 𝑅⃗ whereas the 2nd bracket depends only on 𝑟, so that we can
rewrite Eq.(2.41) into:
2
1
2R Φ( R) ER
2M Φ( R)
2
2R Φ( R) ER Φ( R) Center of mass Energy 2.42
2M
And
2
1
2r r V (r ) Er
2 r
2
2r r V (r ) r Er r Relative motion of Energy 2.43
2
Eq. (2.43) is known as Radial Equation
92
2.2.1. Solution of the Center of mass Equation for the Hydrogen Atom
The solution to Eq. (2.42) is just a free particle of mass M:
For a free particles :
2 d2
2 2
2
2.44
R dR
R
Substitute Eq. (2.44) into Eq. (2.42), we obtain:
2
d2
Φ( R) ER Φ( R) 2.45
2M dR 2
2M
Multiply both side of Eq. (2.45) by 2
,
d2 2M
2
Φ( R) 2 ER Φ( R) 2.46
dR
From photon energy theorem we have:
P2
ER R , PR k
2M
k
2
2M
2
k2
ER 2.47
2M
Substituting Eq. (2.47) into Eq. (2.46), we obtain:
d2 2M 2 k 2
Φ( R ) Φ( R)
dR 2 2
2M
d2
2
Φ( R) k 2Φ( R) 2.48
dR
Taking the square root both side of Eq. (2.48), we obtain:
d2
Φ( R) k 2 Φ( R)
dR 2
d
Φ( R) 1 k 2 Φ( R), but 1 i
dR
i k 2 Φ( R)
d
Φ( R) ikΦ( R)
dR
dΦ( R)
ikdR 2.49
Φ( R)
93
Taking integral both side of Eq. (2.49), we obtain:
ikdR
dΦ( R )
Φ( R )
ik dR
dΦ( R )
Φ( R )
ln Φ R ikR
ln Φ R
e
ikR
e
Φ R Ae ikR
2.50
Where A is a constant that can be determined by normalization condition and Φ ranges from
0 to 2𝜋
Φ R Φ R d
2
R 1
0
Ae Ae d
2 ikR
1
ikR
0 R
2 ikR 2 ikR ikR
A2 d R A2 dR 1
ikR
0 e e 0 e
2
A2 1, but 1
0 0
0 ed R e
2
A2 d R 1
0
2
A2 R 0 1
2 A2 1
1
A2
2
1
A 2.51
2
Put Eq. (2.51) into Eq. (2.50) we obtain the solution to center of mass equation:
Φ R 1
2
e
ikR
2.52
94
2.3. Solution of the Radial Equation (relative motion) for the Hydrogen Atom
We can rewrite the radial equation of Eq. (2.43), in convenient form.
The variables in Eq. (2.46) cannot be separated in the Cartesian coordinates of the electron
relative to the proton and are replaced by the spherical coordinate (𝑟, 𝜃, 𝜙) and the Laplacian
operator ∇2 is transformed into spherical polar coordinate by using the equations:
2 2 2
2 2 2
2
x y z
r
2r 2.53
x x y y z z
Substituting Eq. (1.46) and Eq. (1.47) and Eq. (1.48) into Eq. (2.53), we obtain Laplacian
after long expression as:
1 2 1 1 2
2 r sin
2
r r r r 2 sin r 2 sin 2
r
1 2 1 1 1 2
2r 2.54
r 2 r r r 2 sin sin 2
r sin
From Eq. (1.74), the angular momentum operator 𝐿̂2 in spherical coordinate is given by
1 1 2
Lˆ2 2
sin sin sin 2 2 2.55
Comparing the term in parenthesis (bracket) of Eq. (2.54) with Eq. (2.55), the laplacian can
be written as:
1 2 Lˆ2
2 r 2.56
r 2 r r r 2 2
95
Substituting Eq. (2.56) into the Radial Equation, Eq. (2.43), we obtain:
2
1 2 Lˆ2
r V (r ) r Er r , but 2 r
2 2
2 r r r r 2 2
r r
2
1 2 Lˆ2
r r V (r ) r Er r
2 r 2 r r r 2 2
2 1 2 2
Lˆ2
r V ( r ) r Er r
2 r r r 2 r
2
2 2
2 1 2 Lˆ2
r V (r ) r Er r 2.57
2 r r r 2 r
2 2
2.3.1. The angular dependency of solution
Since. (2.57) is the dependency of 𝜃 and 𝜙 and We learned in chapter one, the spherical
Harmonics, 𝑌𝑙,𝑚 (𝜃, 𝜙) are eigen function of 𝐿̂2 ;
Lˆ2Yl , m , l l 1 2Yl , m ,
And they are also eigen functions of 𝐿̂𝑧 ;
LˆzYl , m , m Yl , m ,
2.3.2. Hydrogen Wave function (spherical and radial wave function)
The product of the azimuthal 𝜙, polar𝜃, and radial 𝑟, wave functions are the hydrogen wave
functions.
The product of azimuthal and polar wave functions are the spherical harmonics 𝑌𝑙𝑚 (𝜃, 𝜙), so
the hydrogen wave functions are the product of the radial wave functions 𝑅(𝑟) and Spherical
harmonics.
One can remove the dependency of Eq. (2.57) on 𝜃 and 𝜙 embodied in 𝐿̂2 by using
separable variables as:
96
r R r Yl , m , 2.58
Put Eq. (2.58) into Eq. (2.57), we obtain:S
2 1 2 Lˆ2
r V (r ) R r Yl , m , Er R r Yl , m ,
2 r r r 2 r
2 2
2
1 2 Lˆ2
r R r Yl , m , R r Yl , m , V (r ) R r Yl , m , Er R r Yl , m , 2.59
2 r r r
2
2 r 2
Since from the eigenvalue of angular momentum operator square,
Lˆ2Yl , m , l l 1 2Yl , m , and Eq. (2.59) becomes:
2 1 2 l l 1 2
r V (r ) R r Yl , m , Er R r Yl , m ,
2 r 2
r r 2 r 2
2 1 2 l l 1 2
r V (r ) R r Er R r 2.60
2 r r r 2 r 2
2
2 1 d 2 d l l 1 2
r V (r ) R r Er R r 2.61
2 r 2
dr dr 2 r 2
2 r 2
Multiply both side of Eq. (2.61) by 2 , we obtain:
d 2 d 2 r 2 l l 1 2
2 r 2 2 r 2
r V (r ) R r 2 Er R r
dr dr
2
2 r 2 2
d 2 d 2 r 2 2 r 2
dr dr
r l l 1 V ( r ) R r Er R r 2.62
2 2
97
Remark!
o Throughout this lectures note, we will be use the CGS units (Centimeter, Gram, Second of
system of unit) for the coulombs potential or particles moving in central potential where it is
given by :
e2
V r 2.63
r
o In MKS unit (Mass, Kilogram, Second system of unit) for the coulombs potential or particles
moving in central potential where it is given by :
e2
V r 2.64
4 o r
Put Eq. (2.63) into Eq. (2.62) we obtain:
d 2 d 2 r 2 e 2 2 r 2
r
l l 1 2
R r Er R r
2
dr dr r
d 2 d 2 r 2 e2 2 r 2
r l l 1 R r Er R r
dr dr
2 2
r
d 2 d 2 e2 r 2 r 2
r R r l l 1 R r R r 2 Er R r 2.65
dr dr 2
To evaluate Eq. (2.65), We apply the substitution method:
U r rR r
U r 1 2.66
R r r U r
r
Substituting Eq. (2.66) into Eq. (2.65) we obtain:
d 2 d U r U r 2 e2 r U r 2 r 2 U r
r l l 1 Er 2.67
dr dr r r 2
r 2
r
98
To determine the first term of Eq. (2.67) by using derivative by product rule:
d 2 d U r d 2 d 1
r r r U r
dr dr r dr dr
d 2 d 1
r r U r
dr dr
d 2 11 d
r r U r r 1 U r
dr dr
d 2 2 d
r r U r r 1 U r
dr dr
d 2 1 1 d
r 2 U r U r
dr r r dr
d r2 r2 d
2 U r U r
dr r r dr
d d
U r r U r
dr dr
d d d2
U r U r r 2 U r
dr dr dr
d 2 d U r d2
r r U r 2.68
dr dr r dr 2
Put Eq. (2.68) into Eq. (2.67) we obtain:
d2 U r 2 e2 r U r 2 r 2 U r
r 2
U
r l l 1 2
2
Er 2.69
dr r r r
1
Multiply both side of Eq. (2.69) by :
𝑟
r d2 U r 1 2 e2 r U r 1 2 r 2 U r 1
U r l l 1 Er
r dr 2 r r 2
r r 2
r r
d2 U r 2 e2 r U r 2 r 2 U r
2
U 2
r l l 1 2
2
Er
dr r r2 r2
d2 l l 1 2 e2 2 E
2
U r 2
U r 2
U r 2 r U r 2.70
dr r r
To solve Eq. (2.70), we first look at the limiting cases (asymptotic behavior) where 𝑟 → 𝑜
and 𝑟 → ∞, and investigate the respective solutions of 𝑈(𝑟 → 0) and 𝑈(𝑟 → ∞).
99
2 e2 2 E
In the case of 𝑟 → 0, the term 2
and 2 r in Eq. (2.70) can be neglected, and we have:
r
d2 l l 1
2
U r U r 0 2.71
dr r2
Let to solve Eq. (2.71) by let:
U r r 2.72
Put Eq.(2.72) into Eq. (2.71) we obtain:
d 2 l l 1
r r 0
dr 2 r2
d d l l 1
r r 0
dr dr r2
l l 1
d
dr
r 1
r2
r 0
l l 1
1 r 11 r 0
r2
l l 1
1 r 2 2
r 0
r
1 l l 1 2 r
r r 0, where r 2
r2 r2 r
1 l l 1
r r 0
r2 r2
1 l l 1 0
l 1 or l 2.73
The solution to Eq. (2.71) is given by
U r Ar l 1 Br l 2.74
Where A and B are constants.
Since 𝑈(𝑟) vanishes at 𝑟 = 0, the second terms 𝑟 −𝑙 , which diverges at 𝑟 = 0, must be
discarded.
Thus, for smaller 𝑟, the solution of Eq. (2.71) becomes:
100
U r Ar l 1 2.75
We then consider the other limit, where 𝑟 → ∞. In this case, it is the two terms proportional
1 1
to 𝑟 and 𝑟 2 that can be discarded, and we have:
d2 2 E
2
U r 2 r U r 2.76
dr
To evaluate second ordered differential of Eq. (2.76), by using substitution method:
2 Er
2 2
Let 2.77
2 Er
2
Substituting Eq. (2.77) into Eq. (2.76), we obtain:
d2
2
U r 2U r 2.78
dr
Taking the square rot both side of Eq. (2.78), we obtain:
d2
2
U r 2U r
dr
d
U r U r
dr
dU r
dr 2.79
U r
Integrating both side of Eq. (2.79), we get:
dU r
U r
dr
ln U r r
ln U r r
e e
U r e
r
U r e e 2.80
r r
Since, as 𝑟 → ∞, 𝑒 𝜆𝑟 diverges, it is not physically acceptable because wave function must be
infinite (converges).
101
So, the wave function can be written as :
U r e 2.81
r
The solution to Eq. (2.70) can be obtained by combining Eq. (2.75) and Eq. (2.81):
U r Ar l 1 f r er 2.82
Where 𝑓(𝑟) is 𝑟 − dependent function.
Substituting Eq. (2.82) into Eq. (2.70), we obtain:
d2 l l 1 2 e2 2 E 2 E
2
U
r 2
U 2 U r 2 r U r , where U r Ar l 1 f r e r , 2 2 r , A 1
r
dr r r
d 2 l 1 l l 1 l 1 2 e2 l 1
r f r e r
r f r e r
r f r e r 2 r l 1 f r e r 2.83
dr 2 r2 2
r
To evaluate the first term of differential Equation of Eq. (2.63), by using differentiation by
product rule method:
d2 d d r
Ar f r e Ar f r e
l 1 r l 1
dr 2 dr dr
r f r e r l 1 r l 11 f r e r r l 1
d l 1
dr
d
dr
f r e r r l 1 f r e r
dr
r f r e r l 1 r l f r e r r l 1
d l 1 d
dr
f r e r l 1 f r e r 2.84
d2 d d r
Ar f r e Ar f r e
l 1 r l 1
dr 2 dr dr
d
l 1 r l f r er r l 1 f r er r l 1 f r er
d
dr dr
d2 d d d d
Ar l 1 f r e r l 1 r l f r e r r l 1
2
f r e r r l 1 f r e r 2.84
dr dr dr dr dr
I III
II
102
d d
I l 1 r l f r e r l l 1 r l 1 f r e r l 1 r l f r e r l 1 r l f r e r
dr dr
d l 1 d r l d l 1 d
2
d
II r f r e l 1 r f r e r
r f r e r r l 1 f r e r
dr dr dr dr 2
dr
d d
III r l 1 f r e r l 1 r l f r e r r l 1 f r e r 2 r l 1 f r e r
dr dr
Therefore,
d2
Ar l 1 f r e r I II II
2
dr
B
D
l d r
l l 1 r f r e l 1 r f r e l 1 r f r e
l 1 r r l
dr
E
B A C
d2 l d l 1 d
2
l 1 d
Ar f r e l 1 r
2
l 1 r
f r e r
r
2
f r e r
r
f r e r
2.85
dr dr dr dr
C
D
d
l 1 r l f r e r r l 1 f r e r 2 r l 1 f r e r
dr
F
d2
Ar l 1 f r e r A 2 B 2C 2 D E F
dr 2
d 2 r d
r l 1 e f r 2 l 1 r l 2 r l 1 e r f r 2 l 1 r l l l 1 r l 1 2 r l 1 e r f r
dr 2 dr
d2 d 2 2 l 1 d 2 l 1 l l 1
2
Ar l 1
f r e r
2 f r 2 f r 2
2 f r e r r l 1 2.86
dr dr r dr r r
Where
1
r l r 1l 1 r l 1
r
2.87
1 l 1
l 1
r r 2 l 1
2 r
r
103
Put Eq. (2.86) into Eq. (2.83), we obtain:
d2 2 l 1 d 2 l 1 l l 1
r l 1
2 f r 2 f r
2
2
f r e r
dr r dr
r r
l l 1 l 1 2 e 2 l 1
2
r f 2 r f r e r 2 f r r l 1e r
r e r
r r
d2 2 l 1 d 2 l 1 2 e 2
f r 2 f r 2 f r 0
dr 2 r dr r r
l 1 e 2
d2 l 1 d
f r 0 2.88
2
f r 2 f r 2
dr 2 r dr r
To solve Eq. (2.88) , we use the power series and 𝑓(𝑟) is given by:
f r bk r k 2.89
k 0
Substituting Eq. (2.89) into Eq. (2.88), we obtain:
l 1 e 2
d
k l 1 d k
k
2
k r k bk r 0
2
b r 2 b r 2
dr 2 k 0 dr k 0
k 0
r
l 1 e 2
l 1 k
k k 1 bk r 2 k bk r k 1 2
2
k 2
bk r 0
k 0 r
r
l 1 e 2
kb r k 1 2 kb r k 1 2
l 1 k
k k 1 bk r 2
2
k 2
r
k k r bk r 0
k 0
b r k 1 0
2 l 1 kbk r k 2 2 kbk r k 1 2 l 1 e
2
k k 1 b r
k 0
k
k 2
2 k
2.90
Collect the like power of series and becomes:
104
b r k 1 0
k k 2lk 2k bk r k 2 2 k l 1 e
2
2
2 k
k 0
b r k 1 0
k k 2lk 2k bk r k 2 2 k l 1 e
2
2
2 k
k 0
2 k l 1 e 2 b r k 1 0
k 2lk k bk r k 2
2 2 k
k 0
b r k 1 0
2 k l 1 e
2
k k 2l 1 b r
k 0
k
k 2
2 k
2.91
let we substituting 𝑘 = 𝑘 − 1 in the second terms of Eq. (2.91), we arrive in the following
recursion equation
k 1 l 1 e 2 b r k 11 0
k 0
k k 2l 1 bk r k 2
2 2 k 1
b r k 2 0
2 k l e
2
k k 2l 1 b r
k 0
k
k 2
2 k 1
b r k 2 0
r k 2 2 k l e
2
k k 2l 1 b
k 0
k
2 k 1
k k 2l 1 bk 2 k l e b 0
2
2 k 1
k k 2l 1 bk 2 k l e b
2
2 k 1
k k 2l 1 bk 2 k l e b
2
2.92
2 k 1
we take the ratio of successive coefficient of Eq. (2.92), we obtain
2 k l e
2
2
bk
2.93
bk 1 k k 2l 1
for larger values of k; Eq. (2.93) becomes :
bk 2
2.94
bk 1 k
105
This is the behavior of an exponential series, since the ratio of successive coefficients of the
2x
k
2x
relation e k 0 k!
is given by
2 k 1! 2
k
2.95
k !2k 1 k
This is the asymptotic behavior of Eq. (2.89) is
f r bk r k e 2.96
2r
k 0
Hence the radial solution of Eq. (2.82) becomes:
U r r l 1 e er r l 1er 2.97
2r
From Eq. (2.97), as 𝑟 → ∞, the radial wave function 𝑒 𝜆𝑟 goes to infinite and physically
unacceptable.
2.3.3. Atomic energy level, quantum number
To obtain physically acceptable solutions, the expression for 𝑓(𝑟) or Eq. (2.89) should be
terminate at a certain power of 𝑁
N
f r bk r k 2.98
k 0
This requires that all coefficients 𝑏𝑁+1 , 𝑏𝑁+2 , 𝑏𝑁+3 ⋅⋅⋅ have to vanish.
When 𝑏𝑁+1 = 0, the recurrence formula of Eq. (2.93) becomes :
2 k l e
2
2
bk
, since k N 1
bk 1 k k 2l 1
2 N 1 l e 2
2
bN 1
bN 11 N 1 N 1 2l 1
2 N 1 l e 2
2
, at max imum, bN 1 0,
bN 1
bN N 1 N 1 2l 1 bN
106
2 N 1 l e 2
2
0
bN 1
bN N 1 N 1 2l 1
bN 1 2 N 1 l e 0
2
2
2 N 1 l e
2
2 0
N 1 l e
2
2 0 2.99
2𝜇𝐸
Where 𝜆 = √− ̅
ℎ
From the relation of quantum number 𝑛, radial quantum number, 𝑁 and angular quantum
number 𝑙, we have
n N l 1 2.100
Put Eq. (2.100) into Eq. (2.99), we obtain the relations:
n e
2
2 0
n e
2
2 2.101
Squaring both side of Eq. (2.101), we obtain:
n e
2
2
2
2n2 e
2 4
4
2e4 1 2 En
2 4 2
, but 2 2
n
2 En 2 e4 1
2 4
n2
e4 1
2 En 2
n2
e4 1
En 2
Energy Quantization 2.102
2 n2
107
From Bohr theory of the hydrogen atom, the Bohr radius is given by
2
ao 2.103
e
2
1
2
2 2.104
aoe
Energy Quantization of hydrogen atom is given by:
2
e4 1
e
1
En 2 2 2.105
2 n 2ao n2
We can write 𝜆 in terms of Bohr radius as follow:
2 En 2 e 1
2
2
2 2ao n 2
2
e 1 1
2 2
, Where 2 2
ao n ao e
2
e 2
1 1
ae
o
ao n 2
1 1
ao2 n 2
1
2.106
ao n
2.4. Radial wave function 𝑹𝒏𝒍 (𝒓) of the hydrogen atom
The radial part of the wave function 𝑅𝑛𝑙 (𝑟) depends on two quantum numbers, 𝑛 − principal
quantum number and 𝑙 −orbital quantum number.
The radial wave function 𝑅𝑛𝑙 (𝑟) can be obtained from Eq. (2.66):
U r
Rnl r 2.107
r
We can write Eq. (2.82) in terms of principal and angular momentum as:
108
U r Anl r l 1 f r er 2.108
Put Eq.(2.108) into Eq. (2.107) we obtain:
1
Rnl r Anl r l 1 f r e r
r
Anl r l 11 f r e r
Rnl r Anl r l f r e r 2.109
Put Eq. (2.98) into Eq. (2.109) we obtain:
N
1
Rnl r Anl r l e r bk r k , where
k 0 nao
r N
Rnl r Anl r l e nao
b r
k 0
k
k
2.110
Where 𝐴𝑛𝑙 is a normalization constant.
Eq. (2.110) can be determined by two method:
I. By Straight forward calculation
II. By use of special function
I. Straight forward calculation of 𝑹𝒏𝒍 (𝒓)
Example
1. In the ground state of hydrogen atom, what is the ground state of wave function 𝑅𝑙𝑛 (𝑟)?
Given Required
In ground state n 1, l 0, m 0, N 0 R10 r ?
N n 1 l
11 0
N 0
109
Solution
r N
Rnl r Anl r l e nao
b r
k 0
k
k
r 0
R10 r A10 r e b r
0 ao 0
0
k 0
r
A10 e ao
b0
r
R10 r A10b0 e ao
Where 𝐴10 can be obtained from normalization condition of 𝑅10 (𝑟); using:
n!
2.111
ax
xe dx
n
0 a n 1
0 U (r ) U r dr 0 rR10 (r ) rR10 (r ) dr 1
rA b e rA b e dr 1
r r
10 o
ao
10 o
ao
0
r r
A102 bo2 r 2 e ao
e ao
dr 1
0
2 r
0 U (r ) U r dr A10bo 0 r e dr 1 2.112
2 2 2 ao
To evaluate the integration of Eq. (2.112), we apply integration by substitution method:
2
Let: m 2.113
ao
Substituting Eq. (2.113) into Eq. (2.112) and comparing with Eq. (2.111), we obtain:
mr
A102 bo2 r 2 e dr 1
0
mr 2!
A102 bo2 r2e dr A102 bo2 1
0 m 2 1
n ax n!
xe dx
a n1
1 23 8 1 ao3
10 o m3
A 2 2
b 2 1, m 3
,
ao3 ao3 m3 8
3
A b 2 a8 1
2 2
10 o
o
ao3
A102 bo2 1
4
110
4
A102 bo2 2.114
ao3
Hence, 𝐴10 = 1,
4
bo2
ao3
1
4 4 2 2 3
bo 3 3 3 2ao 2 2.115
ao ao ao 2
3 r
R10 r 2ao 2
e ao
2.116
2. Find 𝑅20 (𝑟) =?
Given Required
n0 R20 r ?
l 0
N n l l 2 1 0 1
Solution
r N 1
Rnl r Anl r l
e nao
b r
k 0
k
k
b r b1r1
r
R20 r A20 r 0 e 2 ao
o
o
r
R20 r A20 e 2 ao
bo b1r 2.117
We can express 𝑏1 in terms of 𝑏𝑜 , and based on Eq. (2.93) we have:
2 k l e
2
2
bk
, since bk b1 , bk 1 bo
bk 1 k k 2l 1
2 k l e
2
2
b1
bo k k 2l 1
111
2 k l 2 e 2
2 2
b1 bo , but ao
k k 2l 1 e2
2
2 k l a
o
bo , if k 1, and l 1
k k 2l 1
2 2
2 1 0 a 2 bo
2 2 1
o
bo
ao 1 1
bo bo , but
11 2(0) 1 2 2 ao 2 ao nao
1 1
bo , n 2
nao ao
1 1 a 2a a 1
bo o 2 o bo o2 bo bo
2ao ao 2ao 2ao 2ao
1
b1 bo 2.118
2ao
Put Eq. (2.118) into Eq. (2.117), we obtain:
r r
R20 r A20 e 2 ao
bo bo
2ao
r r
R20 r A20bo e 2 ao
1 2.119
2ao
Where 𝐴20 can be obtained from normalization condition of 𝑅20 (𝑟) by using Eq. (2.111)
U (r ) U r dr rR
0 0 20 (r ) rR20 (r ) dr 1
r r r r
0
rA20bo e 2 ao 1
A20bo e 2 ao 1
2ao
dr 1
2ao
2
2 r r
1 dr 1
2 2 2
A b 20 o 0 r e 2 ao
2ao
2 r r r2
A202 bo2 r 2 e 2 ao
1 2 dr 1
ao 4ao
0
112
2
r r ao
r 2 r 2 r
A202 bo2 r 2 e ao
dr A202 bo2 r 2 e dr A20 o 0
2 2
b r 2 e
2 ao
dr 1
0 0 ao 4ao
r 1 2 2 3 r ao 1 2 r 1
A202 bo2 r 2 e ao
dr A20bo r e dr 2 A202 bo2 r 4 e 2 aodr 1, let m
0 ao 0 4ao 0 ao
m 2 2 2 4 mr
A20bo r e dr 1, comparing with Eq. 2.111
mr mr
A202 bo2 r 2 e dr mA202 bo2 r 3 e dr
0 0 4 0
2! 3! 4!
m 21 m31 m 41
2! 3! m 2 2 4!
2
A202 bo2 3 mA202 bo2 4 A20bo 5 1
m m 4 m
2! 3! m 2 2 2 4!
A202 bo2 3 m A202 bo2 4 A20bo 5 1
m m 4 m
2! 2 2 3! 1 2 2 4!
A202 bo2 3 A20 bo 3 A20 bo 3 1
m m 4 m
1 2 2 4 1 24 1
A20bo 2! 3! ! 3 A202 bo2 2 6 3 A202 bo2 2 6 6 1
4 m 4 m
3
m
2 1 1
A202 bo2 3 1, but m , and ao3
3
m ao m
A202 bo2 2ao3 1
1 2
A202 bo2 3
, since bo
2ao ao3
2
2 1
A202 3
a
3 2ao
o
4 1
A202 3
a o 2 ao3
1
4 A202
2
1
A202
8
1 1
A20 2.120
8 2 2
113
Therefore put Eq. (2.120) and Eq. (2.115) into Eq. (2.119), we obtain:
2
1 r r 2 ao
R20 r 1 e
2 2 ao 2ao
3
1 r r 2 ao
R20 r 1 e 1.121
2ao3 2ao
2.5. Radial wave function with Laguerre polynomials
N
The polynomial r bk r in Eq. (2.110) is polynomial of degree 𝑁 + 𝑙 𝑜𝑟 𝑛 − 1; since 𝑛 =
l k
k 0
𝑁 + 𝑙 + 1.
This polynomial is denoted by 𝐿𝑁𝐾 (𝑟), is known as the associated Laguerre polynomial, it is the
solution to the Schrödinger equation of Eq. (2.88).
From Eq. (2.88), we have
l 1 e 2
l 1 d
2
d
f r 0 2.122
2
f r 2 f r 2
dr 2 r dr r
The solutions to differential equations of the form of Eq. (2.122 or 2.88) were studied by
Laguerre.
The associated Laguerre polynomial is defined in terms of the Laguerre polynomials of order
k, is given by
dN
Lk r Lk r 2.123
N
dr N
Eq. (2.123) is known as associated Laguerre polynomials
Where
Lk r e
r
d k k r
dr k e
r 2.124
Eq. (2.124) is known as Laguerre polynomials.
We can verify that 𝐿𝑘 (𝑟) and 𝐿𝑁𝐾 (𝑟) satisfy the following differential equation
114
d2 d
r
dr 2 L r 1 r dr L r k L r 0
k k k
2.125
d2 d
L r N 1 r dr L r k N L r 0 2.126
N N N
r
dr 2 k k k
Eq. (2.126) is identical to the hydrogen atom of radial equations of Eq. (2.123).
2.6. Associated Laguerre polynomial
Let us proof Eq. (2.123) in the form of differential equation of Eq. (2.126) by using a change
of variable.
Let
2 2 E
2 r r
2
r , r2 2
2 4 2.127
d d2
dr , dr 2
2 2 2
f (r ) g ( )
Put Eq. (2.127) into Eq. (2.122), we obtain:
l 1 e 2
d 2
f r 2
d f r 2
l 1
2
1
2
f r 0, but
dr 2
r dr r e ao
2
1
l 1
d 2
l 1 d ao
g 2 g 2 g 0
d 2
d
4 2
2 2 2
d2 2 l 1 d 4 1
4 2 g 2 2 g l 1 g 0
d 2
d ao
d2 2 2 l 1 d 4 2 1 1
4 2 g
4 1 g
l 1 g 0, but n
d2 d ao ao
115
d2 2 2 l 1 d 4 2
4 2 g 4 1 g l 1 n g 0
d2 d
d2 2 l 1 d 2
2 2 g 2 1 g l 1 n g 0 2.128
d d
2
𝑟
Multiply both side of Eq. (2.128) by 2𝜆, we obtain;
2 r d2 2 l 1 d 2
2 g 2 1 g l 1 n g 0
2 d 2
d
d2 2 l 1 d 2
r 2 g 2 1 g l 1 n g 0
d d
2
d2 2 l 1 d 2 r
2 r g 2 r 1 g l 1 n g 0, but 2 r
d 2
d
d2 2 l 1 d
g 1 g l 1 n g 0
d 2
d
d2 2 l 1 d
g g l 1 n g 0
d2 d
d2 d
g 2 l 1 g l 1 n g 0 2.129
d 2
d
We can rewrite Eq. (2.129) in the form of Eq. (2.126) as:
d2 d
2 g 2l 1 1 g n l 2l 1 g 0 2.130
d d
Since Eq. (2.126) and Eq. (2.130) are identical, then the solution to Eq. (2.122) are given by
the associated Laguerre polynomials as;
L L 2r , 2.131
2l 1
2 r
N
k n l
116
The radial wave function 𝑅𝑛𝑙 (𝑟) of hydrogen atom is given by
l
2r
L
r
Rnl r N nl 2.132
2l 1
2r
nao
e nao
n l nao
Where 𝑁𝑛𝑙 is a constant obtained by normalizing the radial function 𝑅𝑛𝑙 (𝑟):
r 2 Rnl r dr 1 2.133
0
Using the normalization condition of the associated Laguerre function, we obtain:
2n n l !
3
e L
2l 1 2
2.134
2l
e d n l 1!
2
0 n l
After a long expression, a constant 𝑁𝑛𝑙 is given by
n l 1!
3
2 2
N nl 2.135
2n n l !
3
nao
Put Eq. (2.135) into Eq. (2.132), we obtain;
n l 1! 2r r na 2l 1 2 r
3 l
2
L nl na
2
Rnl r 3 e o
nao 2n n l ! nao
o
2 n l 1 ! 2r
3 l
L
r
Rnl r 2.136
2 l 1
3
2r
nao 2n n l ! nao
e nao
n l nao
First six Laguerre polynomials
Lk r e
r d k k r
dr k e
r
For k 0 , Lo r e
r d 0 0 r
dr 0 r r r r
r e e e e e 1
0
2.137
For k 1 , L r e
1
r d
dr
re
r
e
r
e r
re
r
r r
e r e re
r
e
e re
0 0
117
For k 1 , L r 1 r
1
2.138
For k 2 , L2 r e
r d 2 2 r
dr 2
r e e
r d d
dr dr
r
r2e
d
2r e r 2 e
r r
e
r
dr
r d
e
dr
r
2r e
d 2 r
dr e
r
e 2e 2r e 2r e r 2 e
r
r r r r
e 2e 2r e 2r e r 2 e
r r r r r
e 2e 4r e r 2 e
r r r r
r r r
2e re 4r e re r 2 e
r
e
2e 4r e r 2 e
0 0 0
For k 2 , L r 2 4r r
2
2
2.139
For k 3 , L r 6 18r 9r r
3
2 3
For k 4 , L r 24 96r 72r 16r r
4
2 3 4
2.140
For k 5 , L r 120 600r 600r 200r
5
2 3
25r 4 r 5 2.141
118
First few associated Laguerre polynomials
dN
L
N
k
r N Lk r
dr
d0
For N 0 and k 0 , L0 r L0 r 1 2.142
0
dr 0
d d
For N 1 and k 1 , L1 r L1 r 1 r 1 2.143
1
dr dr
d
For N 1 and k 2 , L 2 r L2 r
1
dr
d
dr
2 4r r 2
For N 1 and k 2 , L 2 r 4 2r 2.144
1
d2 d2
For N 2 and k 1 , L1 r 2 L1 r 2 1 r 0 2.145
2
dr dr
d2 d2
2
For N 2 and k 2 , L 2 r 2 4r r 2 2 2.146
2
2
L2 r
dr dr
For N 1 and k 3 , L 3 r 18 18r 3r 2 2.147
1
For N 2 and k 3 , L 3 r 18 6r 2.148
2
For N 3 and k 3 , L 3 r 6 2.149
3
For N 1 and k 4 , L 4 r 96 144r 48r 2 4r 3 2.150
1
For N 2 and k 4 , L 4 r 144 96r 12r 2 2.151
2
For N 3 and k 4 , L 4 r 24r 96 2.152
3
For N 4 and k 4 , L 4 r 24 2.153
4
119
The first few radial wave functions 𝑹𝒏𝒍 (𝒓) of the hydrogen atom
2 n l 1! 2r
3 l
L
r
Rnl r
2 l 1
3
2r
nao 2n n l ! nao
e nao
nl nao
For n 1 and l 0 ,
1 1!
3 0
2 2r
e L
r
R10 r
0 1 2 r
ao
ao 2 1 0 !
3 1 0 ao
ao
3
2 0!
, but L 1
r
1 2r 1 2r
3 e L
ao
ao 2 1!
1 ao 1 ao
8 1 r ao 4 r 2 r 2 r
e 1 3 e ao 3 e ao
e ao
ao3
3 1
ao 2 ao ao 2
2 r r
R10 r 2.154
3
3 e ao
2ao 2 e ao
ao 2
For n 2 and l 0 ,
2 2 0 1 ! 2r
3 0
L
r
R20 r
1
3
2r
2ao 2 2 2 ! 2ao
e 2 ao
2 2 ao
1 2 1! r 2 a 1
3
, but L r 4 2r, L 4 2 ar
1
r 1 r
3 e L2
o
ao 4 2!
ao 2 2 ao
o
1 r r
4 2 e 2 ao
32ao3 ao
1 r r
4 2 e 2 ao but 32 4 2
32ao3 ao
1 r r
4 2 e 2 ao
4 2ao3 ao
1 r r
4 2 e 2 ao
4 2a ao
3
o
4 r r 2 ao
1 e
4 2ao3 2ao
1 r r 2 ao
R20 r 1 e 2.155
2ao3 2ao
120
For 𝑛 = 2 and 𝑙 = 1,
2 2 1 1 ! 2r
3 1
L
r
R21 r
3
3
2r
2ao 2 2 2 1! 2ao
e 2 ao
3 2 ao
3
1 0! r r 2 a 3
, but L r 6, L 6
3
3
3 e o L3
r r
ao 4 3! ao
ao 3 3 ao
3
1 1 r r 2a
e o 6
ao 4 6
3
ao
1 r r 2a 1 r r 2a
6 e o 6 e o , but 864 6 24
864ao3 o
a 864ao3 ao
6 r r 2a
e o
6 24a ao
3
o
1 r r 2a
e o , again, 24 2 6
24ao3 ao
1 r r 2a
e o
2 6ao3 ao
1 r r 2a
R21 r e o 2.156
6a 2ao
3
o
2 2r 2r 2 r 3ao
For n 3 and l 0, R30 r 2 e 2.157
3 3ao3 3ao 27 a0
8 r r r 3ao
For n 3 and l 1, R31 r 1 e 2.158
9 6a 6ao 3ao
3
o
4 r r 3a
For n 3 and l 2, R32 r e o 2.159
9 3a o
3
o
3a
121
2.7. Eigen Values, Quantum Numbers and Degeneracy
Each quantum state of hydrogen atom is specified with three quantum states; 𝑛 (the principal
quantum number), 𝑙(the angular quantum number of electron), and 𝑚 (the z component of
the electrons angular momentum or azimuthal quantum number).
1. 𝒏 −principal quantum number:
Specifies the energy of orbital.
It represents the energy of the state of the electron and can take a value of any
positive integers.
All atomic orbitals with the same value of 𝑛, have the same energy and belong to
the same shell.
2. 𝒍 −Orbital angular momentum quantum number.
It basically gives the shape and size of the cloud in which the electron is most
likely found
Measure of the rate at which the electron circulates around the nucleus, which
defined the shape of the orbital.
l 0,1, 2, n 1 2.160
Where 𝑛 −is different values of 𝑙 for any given 𝑛
Example, an atom with a principal quantum number of 𝑛 = 3 has three orbital
quantum numbers 𝑙 = 0, 1 and 2.
Orbitals of a shell fall into 𝑛 groups called subshell.
Wave function with :
𝑛 = 1, 𝑙 = 0 is referred to as 𝑠 −orbital
𝑛 = 2, 𝑙 = 1 is referred to as 𝑝 −orbital
𝑛 = 3, 𝑙 = 2 is referred to as d 𝑑 −orbital
𝑛 = 4, 𝑙 = 3 is referred to as 𝑓 −orbital
The several of 𝑙 have been given special names from the spectroscopic notation.
𝑙 o 1 2 3 4 5 6
letter s p d f g h i
Name Sharp Principle Diffuse Fine (fundamental) - - -
122
First four letters arose in pre-quantum atomic spectroscopy for classifying emission line and
stands for sharp, principal, diffuse and fine.
3. 𝒎𝒍 −Magnetic quantum number
If the shape, type and size of the orbital is described by the orbital quantum number,
then the orientation or direction of the orbital in the three dimensional space is
related to the magnetic quantum number.
Indicates the orientation or direction of the angular momentum around the
nucleus.
Distinguishes the different orbitals within a subshell, 𝑚𝑙 = 𝑙, 𝑙 − 1,⋅⋅⋅ −𝑙, and
there are 2𝑙 + 1 values of 𝑚𝑙 for a given value of 𝑙.
For example, for an electron in orbital 𝑙 = 1, the possible quantum numbers are
𝑚𝑙 = −1, 𝑚𝑙 = 0 𝑎𝑛𝑑 𝑚𝑙 = +1.
The fact that any orbital has a certain number of orientations in space is known as
space quantization.
123
Table: Relationship among values of 𝑛, 𝑙, 𝑚𝑙 through 𝑛 = 5
𝑛 shel Possible value Subshell Possible value of 𝑚𝑙 Number of orbital in Degeneracy, 𝑔𝑛
l of 𝑙 designation ml l , l 1, , 0, l 1, l subshell (Number of Or Energy level
l n 1 orbits 2
(orbital name) Total number of e 1
ml 2l 1 orbitals in shell En
2ao n 2
1 𝐿 0 1𝑠 0 1 1 𝑒2
−
2𝑎𝑜
2 0 2𝑠 0 1
𝐾 𝑒2
1 2𝑝 1, 0, −1 3 4 − 8𝑎
𝑜
3 𝑀 0 3𝑠 0 1
𝑒2
1 3𝑝 1, 0, −1 3 9 − 18𝑎
𝑜
2 3𝑑 2, 1, 0, −1, −2 5
4 𝑁 0 4𝑠 0 1
𝑒2
1 4𝑝 1, 0, −1 3 −
32𝑎𝑜
2 4𝑑 2, 1, 0, −1, −2 5 16
3 4𝑓 3, 2, 1, 0, −1, −2, −3 7
5 0 5𝑠 0 1
𝑒2
1 5𝑝 1, 0, −1 3 −
50𝑎𝑜
2 45 2, 1, 0, -1, -2 5 25
3 5𝑓 3, 2, 1, 0, -1, -2, -3 7
4 5𝑔 4, 3, 2, 1, 0, -1, -2, -3, -4 9
124
2.7.1. Degeneracy of Hydrogen atom
Degeneracy is used in quantum mechanics to mean of “equal energy”.
It usually refers to electron energy levels or sublevel.
The number of different states of equal energy is called “the degree of degeneracy or just
degeneracy”
The energy depends only on the principal quantum number 𝑛, and they are degenerate in
𝑙 and 𝑚𝑙 means that each energy eigenvalue is degenerate.
For every value of 𝑙, there are 2𝑙 + 1 value of 𝑚𝑙 , and for every value of 𝑛, there are 𝑙 from
0 up to 𝑛 − 1.
Which means that for a fixed 𝑛, the total number of possible energy eigenstate (𝑛𝑙𝑚) or the
degeneracy for a certain 𝑛 is given by:
𝑛−1
Degeneracy = 𝑔𝑛 = ∑(Degeneracy in 𝑚𝑙 ) (2.161)
𝑙=0
The degeneracy in 𝑚𝑙 is the number of states with different value of 𝑚𝑙 that have the same
value of 𝑙 and (2𝑙 + 1) possible 𝑚𝑙 states or degeneracy for a particular value of 𝑙.
𝑛−1
Degeneracy = 𝑔𝑛 = ∑(2𝑙 + 1) = 𝑛2 (2.162)
𝑙=0
Moreover, each electron also carries a spin degree of freedom, measured along a given axis,
1 1
this spin can a either be spin up ( 𝑚𝑠 = 2 ) or spin down (𝑚𝑠 = − 2).
Including this spin, the total degeneracy of states with energy 𝐸𝑛 is given by:
Degeneracy = 𝑔𝑛 = 2𝑛2 (2.163)
125
Example
1. Prove that the degeneracy of the 𝑛𝑡ℎ energy level in the Hydrogen atom is 𝑛2 (disregarding
electron spin). Use the fact that the hydrogen states are labeled by three quantum numbers,
𝑚, 𝑙 𝑎𝑛𝑑 𝑛, where −𝑙 ≤ 𝑚 ≤ 𝑙 𝑎𝑛𝑑 0 ≤ 𝑙 < 𝑛
Solution
n 1
D g n 2l 1
l 0
n 1
1 2l 1
l 1
n 1 n 1
g n 1 2 1 2.164
l 0 l 1
From Gaussian summation relation:
n 1
c dk 2 2c d n 1
n
2.165
k 0
c c c c c c n times cn
i 1
2.166
n 1
1 n 1
l 1
2.167
n
n n 1
i 1 2 3 n
i 1 2
2.168
n 1
n n 1
l
l 1 2
2.169
Put Eq. (2.167) and Eq. (2.169) into Eq. (2.164) we obtain:
n n 1
gn 1 2 n 1
2
1 n2 n n 1
gn n2 2.170
126
2. The number of degenerate orbitals of a hydrogen like atom with principal quantum number
𝑛 = 6 is
A. 12 B. 6 C. 72 D. 36
Solution
If 𝑛 = 6:
𝑙 =𝑛−1 0 1 2 3 4 5
Subshell 𝑠 𝑝 𝑑 𝐹 𝐺 𝐻
Number of orbital in subshell 1 3 5 7 9 12
𝑚𝑙 = (2𝑙 + 1)
Degeneracy, 𝑔𝑛 or total number of orbitals in shell is
D g6 1 3 5 7 9 12 36 or
D n 2 62 36
Radial probability distribution
The radial probability is the probability of finding the electron at a distance between
𝑟 𝑎𝑛𝑑 𝑟 + 𝑑𝑟 from the nucleus.
In general,
nlm r, , Rnl r Ylm ,
Probability density for finding electron in given volume element, d𝜏, is
127
nlm r , , d nlm r , , nlm r , , r 2 dr sin d d
2
Rnl r Ylm , Rnl r Ylm , r 2 dr sin d d
Rn'l ' r Rnl r Yl ' m ' , Ylm , r 2 dr sin d d
nlm r , , d Rnl r Yl ' m ' , Ylm , r 2 dr sin d d
2 2
Where
d dV dxdydz r 2 sin drd d Volume element
x r sin cos , y sin sin , z r cos
2
dx dy dz r , , d sin d r 2 dr r , ,
0 0 0
Fig: The volume element 𝑑𝑉 in spherical coordinates
The parallelepiped approaches a rectangular box as 𝑑𝑟 → 0, 𝑑𝜃 → 0, 𝑑𝜙 → 0, so that the
volume element from above figure is:
128
dV LWH
r sin d rd dr
dV r 2 sin drd d
Integrate over all values of 𝜃 and 𝜙 to calculate probability of finding electron inside spherical
shell of thickness 𝑑𝑟 at distance r from origin
2
nlm r , , d r 2 Rnl r dr d Ylm , Ylm , sin d
2 2
0 0
Hence, from the normalization condition of spherical harmonic we have
2
Y , Y , sin d d d Ylm , Ylm , sin d l ' m ' lm l ' m ' lm
l 'm' lm 0 0 0
If the spherical wave function (Eq. ()) have been properly normalized to unity, the radial
probability density 𝑝𝑛𝑙 (𝑟) is given by:
2
pnl r r 2 Rnl r dr d Ylm , Ylm , sin d
2
0 0
1
pnl r r 2 Rnl r dr
2
Probability density r 2 Rnl r dr is called radial distribution function.
2
129
Chapter 3
3. Perturbation method
Perturbation theory is an extremely important method of seeing how quantum system will be
affected by a small change in the potential.
Energy spectrum
Figure 3.1: Perturbed Energy Spectrum
Perturbation means small disturbance.
In this case where the deviation between two problems is small.
To analyze a systems energy, if we don’t know the exact way of solution, then we can study
the effects of external factor (perturbation) on the Hamiltonian.
Perturbation theory gives method for learning problem that solved exactly to the one that
cannot.
Perturbation theory is based on the assumption that the problem we wish to solve in some
sense only slightly different from a problem that can be solved exactly.
When the deviation between two problems is small, the perturbation is suitable for calculation
of deviation.
130
The application of the approximation method to the study of the stationary state consists of
̂ that
the energy eigenvalue 𝐸𝑛 and the eigenstate |𝜓𝑛 ⟩ of a time independent Hamiltonian 𝐻
does hold exact solutions:
Hˆ n En n 3.1
̂ is to complicated, both |𝜓𝑛 ⟩ and 𝐸𝑛 are unknown.
Since 𝐻
We have to split the Hamiltonian into two parts
1. Hamiltonian whose solution we know exactly, 𝐻 𝑜 :
Hˆ o no Eno no 3.2
Where 𝜓𝑛𝑜 and 𝐸𝑛𝑜 orthonormal Eigen function and eigenvalue.
2. Hamiltonian we don’t know the exact solutions, or the perturbation, 𝐻1 .
Hˆ n En n
In one dimensional harmonic oscillator, the Hamiltonian is given by:
2
d2 1 2
Hˆ kx cx3 dx 4 3.3
2m dx 2 2
Eq. (3.3) is similar to harmonic oscillator for which we know the solutions:
2
d2 1 2 2
d2
Hˆ 0 kx V x 3.4
2m dx 2 2 2m dx 2
If the two constant c and d are small, we would expect the wave function and related energies
to be close in the form to the harmonic oscillator solutions.
̂ can be written as:
The total Hamiltonian 𝐻
Hˆ Hˆ o Hˆ 1 3.5
Where:
̂ → Total Hamiltonian
𝐻
̂ 𝑜 → Free or unperturbed Hamiltonian
𝐻
̂1 → Perturbed Hamiltonian
𝐻
𝜆 → Perturbed parameter (strength of the perturbation), 0 ≪ 𝜆 ≪ 1
When 𝜆 = 0, we have the unperturbed system and for 𝜆 = 1, the perturbation is fully turned
on.
This form of perturbation theory is called Rayleigh Schrödinger perturbation theory.
131
3.1. Types of perturbation Theory
i. Time independent perturbation Theory (TIPT)
TIPT→ will cause shift or split in the energy level.
ii. Time dependent perturbation Theory (TDPT)
TDPT→ will cause transition among with energy level.
3.1.1. Time independent perturbation Theory (TIPT)
There are two types of TIPT:
A. Non degenerate perturbation theory.
Different wave function having different energy (eigenvalue of energy).
If the system is linearly only one eigenvalue for one eigen function.
B. Degenerate perturbation Theory
Different wave function having the same energy (eigenvalue).
All having the same energy
Time independent, non- degenerate perturbation Theory (“Rayleigh Schrödinger”)
The Schrödinger equation for the perturbed state is given by:
Hˆ n Hˆ o Hˆ 1 n En n 3.6
Since the Hamiltonian depends on the parameter 𝜆, both the Eigen functions and eigenvalues
will depends on 𝜆.
Expanding |𝜓𝑛 ⟩ and 𝐸𝑛 in a series of power of 𝜆, by using McLaurin Theory;
n n 0 n1 2 n 2 3.7
En En 0 En1 2 En 2 3.8
132
(1) (1)
The term 𝜓𝑛 and 𝐸𝑛 are called the first order corrections to wave function and Energy
respectively and
(2) (2)
The 𝜓𝑛 and 𝐸𝑛 are the second order corrections and so on.
Put Eq. (3.7) and Eq. (3.8) into Eq. (3.6), we obtain:
Hˆ o
Hˆ 1 n En n
Hˆ o
Hˆ
1
n
0
n1 2 n 2 En 0 En1 2 En 2 n
0
n1 2 n 2 3.9
I II
I Hˆ o Hˆ 1
n
0
n1 2 n 2
Hˆ o n 0 Hˆ 1 n 0 Hˆ o n1 2 Hˆ 1 n1 2 Hˆ o n 2 3 Hˆ 1 n 2
Hˆ o n 0 Hˆ 1 n 0 Hˆ o n1 2 Hˆ 1 n1 Hˆ o n 2 3 Hˆ 1 n 2
3.10
II En 0 En1 2 En 2
n
0
n1 2 n 2
En 0 n 0 En1 n 0 2 En 2 n 0 En 0 n1 2 En1 n1 3 En 2 n1
2 En 0 n 2 3 En1 n 2 4 En 2 n 2
II En 0 n 0 En1 n 0 En 0 n1 2 En 2 n 0 En1 n1 En 0 n 2
3 En 2 n1 En1 n 2 4 En 2 n 2
3.11
Equating Eq. (3.10) with Eq. (3.11) and rearrange and collect terms according to like powers
of 𝜆.
I II
E 0 0 E 1 0 En 0 n1
Hˆ o 0 Hˆ 1 0 n n
n n
Hˆ o n1
n
n
2 2 0
En n En n
1 1
En 0 n 2
3.12
2 Hˆ 1 n1 Hˆ o n 2 3 Hˆ 1 n 2
3 2 1 1 2 4 En 2 n 2
En n En n
From Eq. (3.12), zero order equation is given by:
Hˆ o n 0 En 0 n 0 3.13
133
The first order Equation is given by:
Hˆ 1 n 0 Hˆ o n1 En1 n 0 En 0 n1
Hˆ 1 n Hˆ o n En n En n
0 1 1 0 0 1
3.14
Or
Hˆ n En n En n Hˆ n
o 1 0 1 1 0 1 0
Hˆ E E Hˆ
o
n
0
n
1
n
1 1
n
0
3.15
The second order Equation is given by:
2 Hˆ 1 n1 Hˆ o n 2 2 En 2 n 0 En1 n1 En 0 n 2
Hˆ n Hˆ n En n En n En n
1 1 o 2 2 0 1 1 0 2
3.16
Or
Hˆ n En n En n En n Hˆ n
o 2 0 2 2 0 1 1 1 1
Hˆ E
o
n
0
n
2
En 2 n 0 En1 Hˆ 1 n1 3.17
(𝟏)
The First order correction to Energy 𝑬𝒏
(𝟏)
To find the first order to Energy 𝑬𝒏 , we multiply the first order equation or Eq. (3.15) from
the left side by n 0
n 0 Hˆ o En 0 n1 n 0 En1 Hˆ 1 n 0
n 0 Hˆ o n1 n 0 En 0 n1 n 0 En1 n 0 n 0 Hˆ 1 n 0 , but n 0 Hˆ o n 0 En0 3.19
The first term of the left side of Eq. (3.19) can be written in the form of zero order equations
and convert ket into bra eigenstate
Hˆ o n 0 En 0 n 0
Hˆ E
o
n 0 n
0
n 0
n 0 Hˆ o n 0 En 0 3.20
134
Put Eq. (3.20) into Eq. (3.19), we obtain:
n 0 En 0 n1 n 0 En 0 n1 n 0 En1 n 0 n 0 Hˆ 1 n 0 ,since Hˆ o hermitian
En 0 n 0 n1 En 0 n 0 n1 En1 n 0 n 0 n 0 Hˆ 1 n 0
0 0 1
0 En1 n 0 Hˆ 1 n 0
En1 n 0 Hˆ 1 n 0 3.21
Or
En1 n 0 Hˆ 1 n 0 dx 3.22
(𝟏)
First order correction to the wave function 𝝍𝒏
To find the first order to the wave function, we multiply the first order equation or Eq. (3.15)
from the left side by m 0
m 0 Hˆ o En 0 n1 m 0 En1 Hˆ 1 n 0
m 0 Hˆ o n1 m 0 En 0 n1 m 0 En1 n 0 m 0 Hˆ 1 n 0
m 0 Em 0
m 0 Em 0 n1 m 0 En 0 n1 m 0 En1 n 0 m 0 Hˆ 1 n 0
Em 0 m 0 n1 En 0 m 0 n1 En1 m 0 n 0 m 0 Hˆ 1 n 0
0
0 0 1 0 0 1 0
E m m n E n m n m Hˆ 1 n 0 Re arrage
m 0 Hˆ 1 n 0 En 0 m 0 n1 Em 0 m 0 n1
m 0 Hˆ 1 n 0 En 0 Em 0 m 0 n1
m 0 Hˆ 1 n 0
m n 0 1
3.23
En 0 Em 0
To find derivation for an expression for n1 , we employ the identity operator or complete
set in the expressions of unperturbed system or zero order eigenfumction.
135
n1 Iˆ n1 m 0 m0 n1 , 3.24
m n
Put Eq. (3.23) into Eq. (3.24), we obtain:
n1 Iˆ n1 m 0 m 0 n1
m n
m 0 Hˆ 1 n 0
E E
n
0
m
0
m 0 Hˆ 1 n 0
n 1
m 0
3.25
m n En Em
0 0
Eq. (3.25) is shows that the first order correction to wave function
(𝟐)
The second order correction to Energy 𝑬𝒏
(2)
To find the second order correction to Energy 𝐸𝑛 , we multiply the second order equation or
Eq. (3.17) from left side by n 0
n 0 Hˆ o En 0 n 2 n 0 En 2 n 0 n 0 En1 Hˆ 1 n1
n 0 Hˆ o n 2 n 0 En 0 n 2 n 0 En 2 n 0 n 0 En1 n1 n 0 Hˆ 1 n1
n 0 En 0
n 0 En 0 n 2 n 0 En 0 n 2 n 0 En 2 n 0 n 0 En1 n1 n 0 Hˆ 1 n1
En 0 n 0 n 2 En 0 n 0 n 2 En 2 n 0 n 0 En1 n 0 n1 n 0 Hˆ 1 n1
0 0 1 0
0 En 2 n 0 Hˆ 1 n1
En 2 n 0 Hˆ 1 n1 3.26
Put Eq. (3.25) into Eq. (3.26), we obtain:
m 0 Hˆ 1 n 0
2
En n 0
H ˆ 1 0
m n
m
E E
n
0
m
0
m 0 Hˆ 1 n 0
n H 0 ˆ 1 m 0
mn E E
n
0
m
0
2
m 0 Hˆ 1 n 0
En
2
3.27
m n E E
n
0
m
0
136
Eq. (3.27) is known as the second order correction to Energy.
Example
1. The unperturbed wave function solutions for the infinite square well is given by
2
n 0 ( x) sin na x
a
Find the first order correction to energies for the potential.
Given Required
2
n 0 ( x) sin na x En1 ?
a
V if 0 < x < a
H o
1
0 if a x 0
Solution
En n
0
Hˆ n in discrete form
1 1 0
Hˆ dx in continuous form
En n
1 a 0 1 0
0 n
En1 sin na x Vo sin na x dx
a
2 2
0 a a
sin 2 na x dx
a
Vo 2
0 a
En sin 2 na x dx 3.28
a
1 2Vo
a 0
137
To evaluate Eq. (3.28), by using integration by substitution method:
Let:
n x
u
a
n
du dx 3.29
a
a
dx du
n
Substituting Eq. (3.29) into Eq. (3.28), we obtain:
En1
a
2Vo
a sin 2 u na du
0
a
2Vo a
n a sin 2 udu
0
En 3.30
a
1 2Vo
n sin 2 udu
0
From trigonometric identity, we have:
cos 2 1 2sin 2
2sin 2 1 cos 2
sin 2 1
2 1 cos 2
sin 2 u 1
2 1 cos 2u 3.31
Put Eq. (3.31) into Eq. (3.30), we obtain:
En1 1 cos 2u du
2Vo a
1
n 0 2
a a
du 2 no
2Vo 2V
2 n cos 2udu
0 0
En 3.32
a
u 0 no
1 Vo a V
n cos 2udu
0
To evaluate the 2nd terms of Eq. (3.32), we apply integration by substitution method:
Let
2u x
2du dx 3.33
du dx2
Put Eq. (3.33) into Eq. (3.32), we obtain:
138
En1
a
u 0 2Vno
Vo a
n cos xdx
0
u 0 2Vno sin x 0 , but x 2u
Vo a a
n
u 0 2 no sin 2u 0 , but u
a
Vo a V n x
n a
na x 0 2Vn sin 2na x 0
a a
Vo
n
o
na a 0 2 no sin 2 na a 0
Vo V
n
2 no sin 2n sin 0 , sin 0 0
Vo n a V
n a
Vo 2Vno sin 2n , but sin 2n 0
Vo 2 no 0
V
En Vo
1
3.34
The corrected energy levels are:
En En En En Vo
0 1 0
3.35
(0) 2 𝑛𝜋𝑥
2. The unperturbed wave function for the infinite square well is 𝜓𝑛 (𝑥) = √𝑎 sin ( ). Find
𝑎
the first order correction to energies if the perturbation extended only half-way across with
well as shown in figure below.
𝑎
𝑉𝑜 𝑖𝑓 0 < 𝑥 <
𝐻 (1) = { 2
𝑎
0 𝑖𝑓 < 𝑥 < 𝑎
2
Given Required
139
2
n 0 ( x) sin na x En1 ?
a
V if 0 < x < a 2
H o
1
0 if a 2 x 0
Solution
En1 n 0 Hˆ 1 n 0 n 0 Hˆ 1 n 0 dx
a
En sin na x Vo sin na x dx
a
1 2
2 2
0 a a
sin 2 na x dx
a
Vo
2
2
0 a
En sin 2 na x dx 3.35
a
1 2Vo 2
a 0
To evaluate Eq. (3.35), by using integration by substitution method:
n x n a
Let: u , du dx, dx du 3.36
a a n
Substituting Eq. (3.36) into Eq. (3.35), we obtain:
En 2Vao sin 2 u na du
a
1 2
0
a
2nVoaa sin 2 udu
2
En 2nVo sin 2 udu 3.37
a
1 2
From trigonometric identity, we have:
cos 2 1 2sin 2
2sin 2 1 cos 2
sin 2 1
2 1 cos 2
sin 2 u 1
2 1 cos 2u 3.38
Put Eq. (3.38) into Eq. (3.37), we obtain:
140
1 cos 2u du
1
a
En 2Vo 2
1
n 0 2
a a
du
2Vo 2 2Vo 2
2 n 2 n cos 2udu
0 0
1
3.39
a
a
En Vo
u0 Vo
2 2
n n cos 2udu
0
To evaluate the 2nd terms of Eq. (3.39), we apply integration by substitution method:
Let
2u x
2du dx 3.40
du dx2
Put Eq. (3.40) into Eq. (3.39), we obtain:
En
a
u 02 2Vno cos xdx
a
1 Vo 2
n 0
a a
Vo
n u 02 2Vno sin x 02 ,but x 2u
u 02 2Vno sin 2u 0 , but u
a a
Vo n x
2
n a
0 2Vno sin 2 na x 0
a a
Vo n x 2 2
n a
Vo
n na a2 0 2Vno sin 2 na a2 0
Vo n a
n 2 a 2Vno sin 2 2na a sin 0 , sin 0 0
V2o 2Vno sin n , but sin n 0
V2o 2Vno 0
Vo
En
1
3.41
2
The corrected energy levels are:
Vo
En En En En
0 1 0
(approximate) 3.42
2
141
3. Calculate the first order energy correction for one dimensional harmonic oscillator close to
p2 1 2
Hamiltonian is H kx ax 4 and the ground state wave function is
2m 2
1
k 4 2kx
2
0
n ( x) e
Given Required
p2 1 2
Hˆ kx ax 4 En1 ?
2m 2
Hˆ Hˆ Hˆ
0 1
ˆ 0 p2 1 2
H kx
2m 2
Hˆ 1 ax 4
1
k 4 2kx
2
0
n ( x) e
Solution
En1 n 0 Hˆ 1 n 0 d
k k
kx2 kx 2
1 4 1
4
e 2 ax 4
e 2 dx
0
En k 2 a x e 3.43
1 4 kx 2
1
dx
0
To evaluate the integration of Eq. (3.43), we apply Gaussian integral standard form like:
dx
x2
2 n !
m2
2 n 1
3.44
2n
m2
x e n!
0
3.45
1
Let: 1
m2
k
, m2 k
and m
k
k
2
142
Put Eq. (3.45) into Eq. (3.43), we obtain:
En a k
2 2 dx
x2
1
1 2 m2
x e
0
a k 2
2 2 !
m2
1 2 2 1
2!
a k 2 m2
1 5
4!
2!
a k 432121 12 5 m 5
1
2
a k 12 21 m
1 5
2
5
a k 32
12 m
1 5
2
83 a k m , m
5 1 1
2 2
k
k
5
83 a k
1 1
2 2
k k
5
83 a
1
2 2
83 a k
1 1 5
2
1 2 1 1 2
1 5
1
2 2 k 2
83 a k k
1
2 5
2
1
2
5
2
83 a k
4 4
2 2
83 a k
2 2
83 a k 2
2
En 83 a 2
3.46
1
k
The corrected energy levels are:
En En En , En ground state energy
0 1 0 1
2
1
2 83 a 2
k
En 1
2 1 83 a k
3.47
143
Degenerate Time independent perturbation Theory
Degeneracy: different wave functions having the same eigenvalue (energy).
If the unperturbed state are degenerate, then the dominator En 0 Em 0 in the second order
expression is zero, and unless the numerators m 0 Hˆ 1 n 0 is zero, then perturbation
theory in the way we formulated it fails.
To solving such problems in degenerate perturbation Theory by using two fold degenerate
perturbation theory.
Two fold degeneracy
Suppose we have two states a 0 and b 0 that are degenerate (with the same unperturbed
energy eigenvalue).
Hˆ 0 a 0 En 0 a 0 , Hˆ 0 b 0 En 0 b0 3.48
Then a superposition (linear combination) of these two states is also an eigenstate with the
same eigenvalue.
n 0 a 0 b0 3.49
Where α and β are constants.
Put Eq. (3.49) into first order equation (3.14), we obtain:
Hˆ n Hˆ n En n En n
1 0 0 1 1 0 0 1
Hˆ 1 a 0 b 0 Hˆ 0
n1 En1 a 0 b 0 En 0 n1
Hˆ 1 a 0 Hˆ 1 b 0 Hˆ 0 n1 En1 a 0 En1 b 0 En 0 n1 3.50
144
Multiply Eq. (3.50) from left side by a 0 (take inner product with a 0 ):
a 0 Hˆ 1 a 0 a 0 Hˆ 1 b 0 a 0 Hˆ 0 n1 a 0 En1 a 0 a 0 En1 b 0 a 0 En 0 n1
a 0 En 0
a 0 Hˆ 1 a 0 a 0 Hˆ 1 b 0 a 0 En 0 n1 a 0 En1 a 0 a 0 En1 b 0 a 0 En 0 n1
a 0 Hˆ 1 a 0 a 0 Hˆ 1 b 0 En 0 a 0 n1 En1 a 0 a 0 En 1 a 0 b 0 En 0 a 0 n1
1
n
0 1 0 0
a 0 Hˆ 1 a 0 a 0 Hˆ 1 b 0 En1
Hˆ aa1 Hˆ ab1 En1
Hˆ aa1 En1 Hˆ ab1 0
Hˆ aa1 En1 Hˆ ab1 0 3.51
Again we multiply Eq. (3.50) from left side by b 0 (take inner product with b 0 ):
b 0 Hˆ 1 a 0 b 0 Hˆ 1 b 0 b 0 Hˆ 0 n1 b 0 En1 a 0 b 0 En1 b 0 b 0 En 0 n1
b En 0
0
b 0 Hˆ 1 a 0 b 0 Hˆ 1 b 0 b 0 En 0 n1 b 0 En1 a 0 b 0 En1 b 0 b 0 En 0 n1
b 0 Hˆ 1 a 0 b 0 Hˆ 1 b 0 En 0 b 0 n1 En1 b 0 a 0 En1 b 0 b 0 En 0 b 0 n1
0 0 1 0
b 0 Hˆ 1 a 0 b 0 Hˆ 1 b 0 En1
Hˆ ba1 Hˆ bb
1
En
1
Hˆ ba1 Hˆ bb
1
En1 0
Hˆ ba1 Hˆ bb
1
En 0
1
3.52
We can rewrite Eq. (3.51) and Eq. (3.52) in the form of matrix representation:
Hˆ aa1 En1 Hˆ ab1 0
Hˆ Hˆ E 0
1
ba
1
bb n
1
Hˆ aa1 En1 Hˆ ab
1
Hˆ 1
0 3.53
1
Hˆ bb En
1
ba
145
Or we can rewrite the indices of Eq. (3.53) as:
1
Hˆ 11 En 1
Hˆ 12
1
Hˆ 1
0 3.54
Hˆ 22 En
1 1
21
Or Eq. (3.54) can be written as:
1
Hˆ 11 En 1
Hˆ 12
1
Hˆ 1
0 3.55
Hˆ 22 En
1 1
21
Hˆ E Hˆ E Hˆ Hˆ 0
1
11 n
1 1
22 n
1 1
21
1
12
En1 En1 Hˆ 221 En1 Hˆ 11
1 1 ˆ 1
Hˆ 11 1 ˆ 1
H 22 Hˆ 21
2
H 12 0
En1 Hˆ 221 Hˆ 11
1
En1 Hˆ 11
1 ˆ 1 1 ˆ 1
H 22 Hˆ 21 3.56
2
H 12 0
Let: a 1,
b Hˆ 221 Hˆ 11
1
, and 1 ˆ 1
c Hˆ 11 1 ˆ 1
H 22 Hˆ 21 H 12 3.57
Eq. (3.53) is of the form ax2 bx c 0 , and so it has a solution x b b2 4 ac
2a
Hence, the two new energy eigenvalues of Eq. (3.56) is given by:
Hˆ Hˆ Hˆ Hˆ
2
1 ˆ 1 1 ˆ 1
4 Hˆ 11 H 22 Hˆ 21
1 1 1 1
H 12
11 22 11 22
E
1
n
2
Hˆ Hˆ
1
11
1
22
1
Hˆ 11
2
1
Hˆ 22 1 ˆ 1
2 Hˆ 11
2
1 ˆ 1
H 4 Hˆ 11 1 ˆ 1
H 22 Hˆ 21 H 12
2 2
Hˆ Hˆ Hˆ Hˆ
2
1 ˆ 1
1 1 1 1
Hˆ 21 H 12
11 22
1 1
, where Hˆ 12 Hˆ 21
11 22
2 2
Hˆ Hˆ
2
Hˆ 1 2
2
1
Hˆ 11 Hˆ 22
1 1 1 1
11 22
2 2
1 ˆ 1 ˆ 1 1 2
Hˆ Hˆ 3.58
2
En1 H 11 H 22 Hˆ 12
1 1 1
2
11 22
And
1 ˆ 1 ˆ 1 1 2
Hˆ Hˆ 3.59
2
En 2 H 11 H 22 Hˆ 12
1 1 1
2
11 22
146
We now determine the coefficient 𝛼 and 𝛽 from Eq. (3.55):
1
Hˆ 11 En 1
Hˆ 12
1
1
0
Hˆ 1 Hˆ 22 En
1
21
Multiplying out the matrix gives two equations:
Hˆ E Hˆ 0
1
11 n
1 1
12
Hˆ E Hˆ
1
11 n
1 1
12 3.60
And
Hˆ 211 Hˆ 221 En1 0 3.61
From the normalization constant of states, we have:
1 3.62
2 2
1 3.63
2 2
1 3.64
2 2
I. To determine coefficient 𝛼, we squaring both side of Eq. (3.60), we obtain:
Hˆ E 3.65
2
1 2
Hˆ 12
1 1 2 2
11 n
Put Eq. (3.64) into Eq. (3.65), we obtain:
Hˆ E
2
1 2
Hˆ 12 1
1 1 2 2
11 n
Hˆ E
2
1 1 2 2
Hˆ 12 Hˆ 12
1 1 2 2
11 n
Hˆ E
2
1 1 2 2
Hˆ 12 Hˆ 12
1 1 2 2
11 n
Hˆ 1 E 1
1 2
2
1 2
Hˆ 12 Hˆ 12
2
11 n
1 2
Hˆ 12
2
Hˆ 1 E 1
1 2
2
Hˆ 12
11 n
Hˆ 12
1
3.66
2
1
En 1 2
Hˆ 11 Hˆ 12
1
147
II. To determine coefficient 𝛽, we put Eq. (3.66) into Eq. (3.60), we obtain:
Hˆ E Hˆ
1
11 n
1 1
12
Hˆ E Hˆ 12
1 1
1
11 n
1
,
Hˆ 12
Hˆ E
2
1 2
1
11 n
1
Hˆ 12
1
Hˆ 11 En1 Ĥ12
1
Hˆ 12
Hˆ E
1 2
1 2
Hˆ 12
1 1
11 n
Hˆ E
1 1
11 n
Hˆ E Hˆ
2 2
1 1 1
11 n 12
En Hˆ 11
1
1
3.67
2
1
En 1 2
Hˆ 11 Hˆ 12
1
3.1.2. Time –dependent perturbation Theory
When the Hamiltonian of a system depends explicitly on time, then it does not have eigen
solutions and therefore no stationary states are formed.
However, Time development of the state of the system can be described by directly solving
Schrödinger equation, but this solution will depend on the nature of dependence of
Hamiltonian on time.
Time – dependent perturbation theory is most useful in studying the radiated transition of
atomic system from one quantum state to another.
̂ (1) (𝑡) to an unperturbed Hamiltonian 𝐻
Consider some time- dependent perturbation 𝐻 ̂ (0) that
is itself no depend on time.
The total Hamiltonian is then given by:
Hˆ Hˆ Hˆ t 3.68
0 1
To deal with such a situations, we use the time dependent Schrödinger equation:
i Hˆ 3.69
t
148
Where the ket is generally time varying with n 0 and En , as the energy eigenfunctions
0
and eigenvalues of the time – independent equation as
Hˆ n En n
0
3.70
We expand the solution of the time – dependent Schrodinger equation as:
iEnt
an t e n 3.72
n
Where 𝑎𝑛 (𝑡) is expansion coefficient.
Substituting Eq. (3.72) into Eq. (3.69), we obtain:
Hˆ
iEn t iEn t
an t e n an t e , Hˆ Hˆ Hˆ t
0 1
i
t n
n
n
Hˆ Hˆ t
iEn t iEn t
an t e n an t e 0 1
i
t n
n
n
iEn t iEn t iE t
i n
t n
a t e n
n
n
a t e H n n n
ˆ 0 a t e n Hˆ 1 t
n 3.73
Differentiating Eq. (3.73) from left hand side by using differentiation by product rule.
iEn t iEnt
t a t e an t n an t e H n an t e H t n
ˆ 0 ˆ 1
iEnt iEnt
i e
t
n
n n n
iE iEnt
a e an t n n an t e H n an t e H t n
ˆ 0 ˆ 1
iEnt iEnt iEnt
'
i n e
n n n
i n i an t iE e n an t e Hˆ 0 n an t e Hˆ 1 t n
iEnt iEnt iEnt iEnt
an' e n
n n n n
i n an t i 2 En e n an t e Hˆ 0 n an t e Hˆ 1 t n
iEnt iEnt iEnt iEnt
an' e
n n n n
i n an t En e n an t e Hˆ 0 n an t e Hˆ 1 t n
iEnt iEnt iEnt iEnt
an' e
n n n n
En n
i a t E e a t E e n an t e Hˆ 1 t n
iEnt iEnt iEnt iEnt
an' e n n n n n n
n n n n
i n an t e Hˆ 1 t n 3.74
iEnt iEnt
an' e
n n
149
Multiply both Eq. (3.74) from left side by m and we apply orthonormality condition:
i m n an t e m Hˆ 1 t n
iEnt iEnt
an' e
n n
1 if m n
i a t e mn an t e m Hˆ 1 t n , mn
iEnt iEnt
'
0 if m n
n
n n
i am' t e mm an t e m Hˆ 1 t n
iEmt iEnt
m 1 n
i am' t e an t e m Hˆ 1 t n
iEmt iEnt
am' t i1 a t e m Hˆ 1 t n
iEnt
1
iEmt n
e n
a t e m Hˆ 1 t n
iEmt iEnt
i1 n e
n
a t e m Hˆ 1 t n
iEmt iEnt
i1 n
n
i Em En t
i1 a t e
n
n m Hˆ 1 t n
am' t i1 a t e
n
n
i mk t
m Hˆ 1 t n 3.75
Where we have introduced the notation:
Em En
mn Bohr angular frequency 3.76
Eq. (3.76) shows the transition between state m to state n (Bohr angular frequency).
Eq. (3.75) is the fundamental result of time- dependent perturbation theory.
150
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