Chap 7 Quantum Mechanics and Schrödinger Equation

Lecture notes of Chin-Hsiang Cheng

 Classical Mechanics– find exact positions and velocities of particles.

Atoms, molecules,.

Sir Isaac Newton

(1643 – 1727)
An English mathematician, physicist.

Quantum Mechanics-- find most probable positions and velocities of particles.

Electrons, protons, neurons, phonons,…

Erwin Rudolf Josef
Alexander Schrödinger
(1887 – 1961)
Austrian physicist winning
Nobel Prize 1933 in Physics
with Paul Dirac
 Heisenberg's uncertainty principle

where ħ is the reduced Planck constant, h/(2π)

Werner Heisenberg
(1901 – 1976)
A German theoretical winning the standard deviation of position σx
1932 Nobel Prize in Physics

standard deviation of momentum σp

 Wave-Particle Duality

Louis Victor Pierre Raymond de Broglie

(1892 – 1987)
A French physicist and aristocrat

In 1924, de-Broglie suggested that every moving

particle has a wave associated with it, which is also
known as matter wave. Further, Erwin Schrödinger in
continuation to de Broglie’s hypothesis introduced a
differential wave equation of second order to explain
the wave nature of matter and particle associated to
wave. Seven Dragon Balls
Cloud chamber experiment - particle
Particles
 Waves

Interference or diffraction pattern

 Waves

Electron double-slit experiment

Time-independent Schrödinger equation

∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2 m
+ + 2 + ( E − V )ψ = 0
∂x 2
∂y 2
∂z h2
π 2
∇ψ +
2 8 m
( E − V )ψ = 0
h2
Somethings about the Schrödinger Equation
- Schrödinger equation is analogous to the equation for waves in optics, which assumes that the
particle behaves as wave and yields solution in terms of a function called the wave function Ψ.

- When this equation is solved, it gives two things; namely the wave function Ψ and the energy E,
of the particle under consideration.

- Once the wave function Ψ is known, then everything about the particle is known or can be
deduced from the wave function. Thus, the wave function Ψ is the most important thing, which
itself does not have any physical significance, however the absolute square of Ψ, i.e. |Ψ|2 gives
the probability of finding the particle in a particular region of space at a particular instant of
time.

- The term E in the equation is the energy of the particle depending upon the potential V and
boundary conditions (constraints on the particle), which can be continuous or quantized.

- Quantization of energy of the particle is a remarkable feature of the quantum mechanics i.e. a
particle cannot have any energy or continuous energy, but can have only that permitted energy
described by Schrödinger equation together with the potential V and the boundary conditions.
Complex Numbers

i = −1 a, b: Real

c = a + ib a: real part b: imaginary part --- Rectangular coordinates

c = r eiθ r: magnitude θ: phase --- Polar coordinates

Im

b c
r = 𝑎𝑎2 + 𝑏𝑏 2

r a = rcosθ b = rsinθ
θ = tan-1 (b/a)
θ
Re c = a + ib = rcosθ + i rsinθ = r eiθ
a
Schrödinger time independent equation can be derived from
classical wave equation.
Classical Wave Equation
Ψ
∆Ψ ∆Ψ
As displacement is very small, sinθ = ≅
∆s ∆x x

∆Ψ ∆Ψ 𝜕𝜕Ψ
Force in y-direction at point a = Fsinθ = F ≅F ≅F ∆x
∆s ∆x 𝜕𝜕x

𝜕𝜕Ψ 𝜕𝜕 𝜕𝜕Ψ 𝜕𝜕Ψ 𝜕𝜕 2 Ψ

Force in y-direction at point b = F [ + ( )∆x] = F +F ∆x b
𝜕𝜕x 𝜕𝜕x 𝜕𝜕x 𝜕𝜕x 𝜕𝜕x2 ∆s F

Force balance in y-direction: θ ∆Ψ

a
Ψ
𝜕𝜕 2 Ψ F
∑ 𝐹𝐹𝑦𝑦 = m ay = (ρ ∆x) ρ: mass per unit length ∆x
𝜕𝜕t 2 x

𝜕𝜕Ψ 𝜕𝜕Ψ 𝜕𝜕 2Ψ 𝜕𝜕 2 Ψ
∑ 𝐹𝐹𝑦𝑦 = - F +F +F ∆x = (ρ ∆x)
𝜕𝜕x 𝜕𝜕x 𝜕𝜕x2 𝜕𝜕t 2

𝜕𝜕 2 Ψ 𝜕𝜕 2Ψ 1 𝜕𝜕 2Ψ 𝜕𝜕 2 Ψ 1 𝜕𝜕 2Ψ
= (ρ /F) = i.e. = Wave equation C: wave velocity (C2= F/ρ )
𝜕𝜕x2 𝜕𝜕t 2 C2 𝜕𝜕t 2 𝜕𝜕x2 C2 𝜕𝜕t 2
 Longitudinal wave
𝜕𝜕 2 Ψ ρ 𝜕𝜕 2Ψ
including sound waves (vibrations in
pressure, a particle of displacement,
=( ) 2
𝜕𝜕x2 E 𝜕𝜕t and particle velocity propagated in an
elastic medium) and seismic P-waves
Ψ: longitudinal position relative to equilibrium (created by earthquakes and

𝜕𝜕
2Ψ ρ 𝜕𝜕 2Ψ E: elastic modulus explosions).

=(
𝜕𝜕x2 F ) 𝜕𝜕t 2 Traverse wave
Including wave on a string, seismic
𝜕𝜕 2Ψ ρ 𝜕𝜕 2Ψ S-waves, electromagnetic waves.
=(
𝜕𝜕x2 T ) 𝜕𝜕t 2
Ψ: transverse position relative to equilibrium
T: tension

Rayleigh surface waves in an elastic solid travelling from

Water wave travelling from left to right, the
left to right, the particles travel in counter-clockwise circles.
particles travel in clockwise circles.
It causes the most damage during an earthquake.
The propagation of longitudinal waves in an elastic solid may be described by the wave
equation in which Ψ is interpreted as the longitudinal position relative to equilibrium.
For the longitudinal waves in air (sound wave), the wave function Ψ represents the
density or pressure of the air in which the waves propagate. In such cases, the wave
propagation occurs in 3-D space, and the wave equation can be formulated as

𝜕𝜕 2 Ψ 𝜕𝜕 2Ψ 𝜕𝜕 2 Ψ 1 𝜕𝜕 2 Ψ
+ + =
𝜕𝜕x2 𝜕𝜕y2 𝜕𝜕z 2 C2 𝜕𝜕t 2
Several Particle Wave Relations:

1 K
(1) C = λυ C : Wave velocity λ : Wave length υ : Frequency= 2π m

K
(2) ω = 2πυ ω : Angular frequency= m

(3) E = hυ (Planck–Einstein relation) E : Energy of particle h: Planck constant

h h
(4) λ = = (de Broglie wave equation) P: Momentum of particle (=mv)
mv P
Kinetic energy
2
h h
P= or P2 =
λ λ2
Potential2energy
1P 1 2m (E − V)
(5) Energy of particle E = U + V = + V → P2 = 2m (E – V) → 2=
2 m λ h
2
Separation of Variable Method

Let Ψ(x,t) = f(x)g(t)

2
𝜕𝜕 2 Ψ 1 𝜕𝜕 2 Ψ 1 d2 f(x) 1 1 d g(t) ω2
= → = = constant = - 2
𝜕𝜕x2 C2 𝜕𝜕t 2 f(x) dx2 C2 g(t) dt2 C
Not fun. of t Not fun. of x
1 2m (E − V)
=
1 1 d g(t)
2
ω2 λ 2
h
2
(1) 2 = - 2 → g(t) = A e -iωt
C g(t) dt 2
C
2 2
1 d f(x) ω2 d f(x) 2π 2 2 [2m (E − V) ]
(2) = - 2 → = − f(x) ( ) = − f(x) (2π)
f(x) dx2 C dx2 λ h
2

2
d f(x) 8π2m (E − V)
→ + f(x) [ 2 ]=0 or
dx2 h
2
d f(x) 8π2m
+ 2 (E − V) f(x) = 0
dx2 h
For standing waves that correspond to stationary states of the system, the time-dependency
of the wave function can be ignored. The function f(x) can then be replaced by Ψ, giving the
Schrödinger’s time-independent wave equation for a single particle in one dimension:

2
d Ψ 8π2m
+ 2 (E − V) Ψ= 0
dx2 h

In three dimensions, the Schrödinger’s time-independent wave equation takes the form:

𝜕𝜕 2 Ψ 𝜕𝜕 2Ψ 𝜕𝜕 2 Ψ 8π2m
+ + + (E − V) Ψ = 0 or
𝜕𝜕x2 𝜕𝜕y2 𝜕𝜕z 2 h
2

8π2m
𝛻𝛻 2 Ψ + 2 (E − V) Ψ = 0 Schrödinger’s time-independent wave equation
h

The above equations are time independent and they relate to the equilibrium state of a
system of particles.
Time-independent Schrödinger equation in spherical coordinates
x = rsinθ cosϕ y = rsinθ sinϕ z = rcosθ

1 𝜕𝜕 2 𝜕𝜕Ψ 1 𝜕𝜕 𝜕𝜕Ψ 1 𝜕𝜕 2 Ψ 8π2m

(𝑟𝑟 )+ 2 (sinθ )+ 2 2 + (E − V) Ψ = 0
r2 𝜕𝜕r 𝜕𝜕r r sinθ 𝜕𝜕θ 𝜕𝜕θ r sin θ 𝜕𝜕ϕ2 h
2

In the case of particle wave, the square of the amplitude of the wave function is related to
particle density, or to the probability of finding a particle in a volume element dx dy dz. But
the wave function Ψ may be a complex function. On the other hand, probability must be a
positive real value. Consequently, statistical probability density is expressed by means of the
product of both the wave function and its conjugate:
Ψ 2 dx dy dz = probability
2
Ψ Ψ* = Ψ 2 Ψ = probability density

The expression Ψ 2 dx dy dz can be interpreted as the probability of finding a particle in a

given element of volume of the system. Thus,

� Ψ Ψ∗ 𝑑𝑑𝑑𝑑 = 1 - Normalizing condition

𝑉𝑉
IMPORTANT CHARACTERISTICS OF A WAVE FUNCTION

1. Wave function should be normalized. i.e. it should satisfy the

following condition:

∫𝑉𝑉 Ψ Ψ∗ 𝑑𝑑𝑑𝑑 = ∫𝑉𝑉 Ψ Ψ∗ dx dy dz = 1

2. Wave function should be finite. ∞ probability has no meaning.

3. It should have a single value. (As at particular point, probability

can have only one value.)
Schrödinger time dependent equation can be derived
from Schrödinger time independent equation.
The Schrödinger’s time-independent wave equation gives

2 8π2m
𝛻𝛻 Ψ + 2 (E − V) Ψ = 0
h

2m
𝛻𝛻 2 Ψ + 2 (E − V) Ψ = 0 where ħ is the reduced Planck constant, h/(2π) ---- (1)
ħ

Consider a wave function represented as

Ψ = A e -iωt

where A is amplitude of the wave, ω is angular frequency, and t is the time.

𝜕𝜕Ψ
= - i ω A e -iωt = - i (2πυ) A e -iωt
𝜕𝜕t

As E = hυ (Planck–Einstein relation) ,

𝜕𝜕Ψ 2πE 2πE

=-i( ) A e -iωt = - i ( )Ψ
𝜕𝜕t h h
 2
h 𝜕𝜕Ψ i h 𝜕𝜕Ψ i h 𝜕𝜕Ψ 𝜕𝜕Ψ
EΨ = - = = =iħ
i2π 𝜕𝜕t i 2π 𝜕𝜕t 2π 𝜕𝜕t 𝜕𝜕t

Equation (1) becomes

2m 2m
𝛻𝛻 2 Ψ + 2 EΨ − 2 V Ψ= 0
ħ ħ

2m 𝜕𝜕Ψ 2m
𝛻𝛻 2 Ψ + i ħ − 2 VΨ=0
ħ
2
𝜕𝜕t ħ
2
ħ 2 𝜕𝜕Ψ
− 𝛻𝛻 Ψ + V Ψ = i ħ Schrödinger’s time-dependent wave equation
2m 𝜕𝜕t

2
ħ 2 𝜕𝜕Ψ
with − 𝛻𝛻 + V = H as the Hamiltonian operator. Thus, H[ Ψ ] = i ħ .
2m 𝜕𝜕t

The two legendary equations have a fair connection. The two equations are like statics and
dynamics in classical mechanics, hence, the derivability of the time dependent equation from the
time independent form is much significant.
Standing waves and Traveling waves
 Standing waves
Ψ(x,t)

A standing wave on a circular membrane.

A standing waves in a string – the

fundamental mode and the first 5 A higher harmonic standing wave on a disk
overtones. with two nodal lines crossing at the center.
Eigen-value Problem of Ordinary Differential Equations
1. Boundary-value problems: e.g.
At x =0, u = 0
du
At x=L, = 1.0 BVP is very possible to be an Eigen-value problem!
d𝑥𝑥

2. Initial-value problems: e.g.

At x =0, u = 0
At x =0, u = 1.0
Applications of Schrödinger equation

1. Particles of different motions (different energies) may be treated as though they are
independent of each other so that each particular motion (energy) is then described by
its own Schrödinger equation.

2. According to equation theory, the internal energy of a system are quantized. That is,
only discrete values are possible.
 z
Translational Energy

A particle in a small box with potential energy neglected.

The 3-D Schrödinger’s time-independent wave equation:
c
𝜕𝜕 2 Ψ 𝜕𝜕 2Ψ 𝜕𝜕 2 Ψ 8π2m
+ + + (E − V) Ψ = 0
𝜕𝜕x2 𝜕𝜕y2 𝜕𝜕z 2 h
2 x
y b
a
Let V=0 and the time independent wave function be expressed as

Ψ(x, y, z) = X(x)Y(y)Z(z) V=∞ V=∞

(wall) (wall)
2 2 2
1 d X 1 d Y 1 d Z 8π2m
+ + + E=0
X dx2 Y dy2 Z dz2 h
2

The energy E can be expressed in terms of its components in

each of the three directions:
V=0
E = Ex + Ey + Ez x=0 x=a
Since the energies in the x-, y- and z-directions are independent of each other, the wave
equation may be expressed separately for each direction
2
1 dX 8π2m
+ E𝑥𝑥 = 0
X dx2 h
2

2
1 dY 8π2m
+ E𝑦𝑦 = 0
Y dy2 h
2

2
1 dZ 8π2m
Z dz2 + h2 E𝑧𝑧 = 0

For the x-direction

2
dX 8π2m
2 + 𝑀𝑀E𝑥𝑥 X = 0 where M= 2
dx h

→ X = A sin 𝑀𝑀E𝑥𝑥 x + B cos 𝑀𝑀E𝑥𝑥 x

Boundary Conditions:

(1) At x=0, X = 0 → B=0 and → X = A sin 𝑀𝑀E𝑥𝑥 x

(2) At x=a, X = 0 → A sin 𝑀𝑀E𝑥𝑥 a = 0, A ≠ 0 → sin 𝑀𝑀E𝑥𝑥 a = 0 or

𝑀𝑀E𝑥𝑥 a = nxπ where nx= 1, 2, 3, …. (positive integer)

Therefore,

nx2h2
Ex = where nx= 1, 2, 3, …. (eigen values)
8ma2

and

nxπ
X = Ax sin x (wave function, eigen functions)
a

nx: translational quantum number. Since nx is an integer, the energy Ex can have only certain
discrete values. Thus, the energy of a particle in a box is quantized.
Similarly,

n𝑦𝑦2h2
Ey = 2 where ny= 1, 2, 3, ….
8mb
nyπ
Y = Ay sin y
b

n𝑧𝑧 2h2
Ez = where nz= 1, 2, 3, ….
8mc 2
nzπ
Z = Az sin z
c
The total translational energy and the wave function are then

h2 n𝑥𝑥2
n𝑦𝑦2 n𝑧𝑧 2
E = Ex + Ey + Ez = [ + 2 + 2]
8m a2 b c

nπ nπ nπ
Ψ(x, y, z) = X(x)Y(y)Z(z) = A sin( x x) sin( y y) sin( z z)
a b c

where A is to determine by normalization condition.

Normalization condition:

� Ψ Ψ∗ 𝑑𝑑𝑑𝑑 = � Ψ 2 𝑑𝑑𝑥𝑥𝑥𝑥𝑥𝑥𝑥𝑥𝑥𝑥 = 1
𝑉𝑉 𝑉𝑉

gives

8 8
A= =
abc V

Therefore

8 nπ nπ nπ
Ψ(x, y, z) = sin( x x) sin( y y) sin( z z)
V a b c
 𝟐𝟐
1-D Wave Function Ψ and Ψ
 𝟐𝟐
3-D Wave Function Ψ Plotted in x-y Plane
3-D Wave Function Ψ 𝟐𝟐 Plotted in 3-D Space

211 132 313

 Total Energy
Degree of
n2=nx2+ny2+nz2 Combinations of (nx, nx, nx) (E)
Degeneracy
a=b=c=L
2
3 (1,1,1) 3h 1
2
8mL
2
6 (2,1,1) (1,2,1) (1,1,2) 6h 3
2
8mL
2
9 (2,2,1) (1,2,2) (2,1,2) 9h 3
2
8mL
2
11 (3,1,1) (1,3,1) (1,1,3) 11h 3
2
8mL
2
12 (2,2,2) 12h 1
2
8mL
2
14 (3,2,1) (3,1,2) (2,3,1) (2,1,3) (1,3,2) (1,2,3) 14h 6
2
8mL
2
17 (2,2,3) (3,2,2) (2,3,2) 17h 3
2
8mL
2
18 (1,1,4) (1,4,1) (4,1,1) 18h 3
2
8mL
2
19 (1,3,3) (3,1,3) (3,3,1) 19h 3
2
8mL
 h2
E/( 2) Degeneracy (nx, ny, nz)
8mL

14 g=6 123, 132, 213, 231, 312, 321

12 g=1 222
11 g=3 311, 131, 113

9 g=3 122, 212, 221

6 g=3 211, 121, 112

3 g=1 111 (ground state)

h2
If a=b=c=L, E= [nx2+ny2+nz2]. The particle wave with a trapped particle is quantized;
8mL
whereas that with a free particle is continuous.
Example 1
The 6th energy level of a particle in a 3D Cube box is 6-fold degenerate.
(a) What is the energy of the 7th energy level?
(b) What is the degeneracy of the 7th energy level?
Solution:

17h2
(a) 2
8mL

(b) Three-fold. That is, there are three wavefunctions that share the same energy.
Example 2
Consider a particle trapped in a one-dimensional well of fixed size. Suppose you have a
particle in the ground state. You also have a device allow you to add energy to the particle.
You try to add an infinitesimally small amount of energy, but nothing happens, because only
certain amounts of energy can be gained by the particle. What is the smallest amount of
energy you can successfully transfer?
Solution:
For one-dimensional well, the energy levels are listed as follows

n2h2 h2
n = 1 (ground state) E= 2 = 2
8mL 8mL
n2h2 4h2
n=2 E= 2 = 2
8mL 8mL

4h2 h2 3h2
The smallest amount of energy needed = 2 - 2 = 2
8mL 8mL 8mL

The only way the particle will make the transition from the ground state to the first excited
3h2
state is if something transfers 2 into it, giving the particle just the right amount of
8mL
energy to make the transition.
Example 3
The protons and neutrons of an atom are confined to the nucleus. We will model the nucleus
as an inescapable one-dimensional box of size 10−15 m (typical for atomic nuclei). Give an
estimate of how much energy we would need to move a proton in Helium from the ground
state and up to the next energy level.
Solution:

As in Example 2,
−34
3h2 3(6.626×10 Js)2
J ≅ 6.0 × 108 eV
−11
∆E = 2 = −27 −15 2 = 9.9 × 10
8mL 8(1.67×10 kg) (10 m)

(To make a meaningful comparison, the amount of energy it takes to break a chemical bond
has a typical magnitude of 1 eV. )
 Rotational Energy
To describe rotational motion, it is convenient to use the time-independent Schrödinger equation
in spherical coordinates. Consider a model of a dumbbell diatomic molecule comprising two atoms.
Consider a model of a “dumbbell” diatomic molecule comprising two atoms.
Let the origin of the Cartesian coordinates be located at the
m1 center of mass of the molecule.
z
r1sinθφ̇ Vm1 = V 2 + V 2 = ̇ 2 + (r sinθφ̇ )2 = r (θ)
(r1θ) ̇ 2 + (sinθ φ̇ )2
θ φ 1 1

̇ 2 + (sinθ φ̇ )2
Vm2 = r2 (θ)
r1 r1θ̇

Center The kinetic energy of the molecule can thus be written

θ
of mass
1 1 1 ̇ 2 + (sinθ φ̇ )2 ]
φ x εrot = m1 V2𝑚𝑚𝑚 + m2 V2𝑚𝑚2 = (m1 r12 + m2 r22 )[(θ)
2 2 2
r2
y 1 ̇ 2 + (sinθ φ̇ )2 ]
= 𝐼𝐼 [(θ)
2
m2
where 𝐼𝐼 = m1 r12 + m2 r22 = , the moment of inertia.
 Total length r = r1 + r2 and m1r1 =m2r2
Therefore,

m2 m1
r1 = r , r2 = r
m1 + m2 m1 + m2

m1 m2 2 m1 m2
𝐼𝐼 = m1 r12 + m2 r22 = r = m′ r2 m′ = = Reduced mass of the molecule
m1 + m2 m1 + m2

The time-independent Schrödinger equation in spherical coordinates

1 𝜕𝜕 2 𝜕𝜕Ψ 1 𝜕𝜕 𝜕𝜕Ψ 1 𝜕𝜕 2 Ψ 8π2m

(𝑟𝑟 )+ 2 (sinθ )+ 2 2 + (E − V) Ψ = 0
r2 𝜕𝜕r 𝜕𝜕r r sinθ 𝜕𝜕θ 𝜕𝜕θ r sin θ 𝜕𝜕φ2 h
2

8π2I
0, ⸪ only the rotation around the ε Ψ, ⸪ (1) E = εrot, and V=0 (No potential energy)
2 2 rot
fixed mass center is considered, rh
I
and so r1 and r2 are fixed. (2) m = m′ = 2
r
 1 𝜕𝜕 𝜕𝜕Ψ 1 𝜕𝜕 2 Ψ 8π2I
r2 sinθ 𝜕𝜕θ
(sinθ
𝜕𝜕θ
)+ 2 2
𝜕𝜕 φ2 + 2 2 εrotΨ = 0 or
r sin θ rh

1 𝜕𝜕 𝜕𝜕Ψ 1 𝜕𝜕 2Ψ 8π2I
(sinθ )+ 2 2 + 2 εrotΨ = 0
sinθ 𝜕𝜕θ 𝜕𝜕θ sin θ 𝜕𝜕 φ h

Separation of variable method:

Let Ψ(θ, φ) = Θ(θ)Φ(φ)

sinθ 𝜕𝜕 𝜕𝜕Θ 8π2I 1 𝜕𝜕 2 Φ

(sinθ ) + 2 εrot sin θ= -
2 = constant = m2
Θ 𝜕𝜕θ 𝜕𝜕θ h Φ 𝜕𝜕φ 2

Not fun. of φ Not fun. of θ

1 𝜕𝜕 2Φ
(1) - = m2
Φ 𝜕𝜕φ 2

Φ = C𝑒𝑒 𝑖𝑖mφ = A sin mφ + B cos mφ

(i) Φ = A sinmφ + B cosmφ

Criterion: The function Φ must be single-valued, and must repeat itself at 2π interval. Therefore,

sin mφ = sin m(φ + 2π) = sin mφ cos 2πm + cos mφ sin 2πm

cos mφ = cos m(φ + 2π) = cos mφ cos 2πm - sin mφ sin 2πm

To meet the above criterion, that the conditions cos 2πm =1 and sin 2πm = 0 must be
simultaneously satisfied. This is possible only m is an integer (0, 1, 2, 3,…..).

(ii) Φ = A𝑒𝑒 𝑖𝑖mφ

2π 1
Normalization condition ∫0 ΦΦ∗ 𝑑𝑑φ = 1 gives A = .
2π

1 𝑖𝑖mφ
Therefore, Φ= 𝑒𝑒
2π
 sinθ 𝜕𝜕 𝜕𝜕Θ 8π2I
(2) (sinθ ) + 2 εrot sin2θ = m2
Θ 𝜕𝜕θ 𝜕𝜕θ h

8π2I d dx d d
Let λ= 2 εrot , x=cosθ and y(𝑥𝑥) = Θ(θ) ( = = −sinθ and sin2θ = 1 − x2 )
h dθ dθ dx dx

These substitutions lead to

sinθ 𝜕𝜕 𝜕𝜕Θ
(sinθ ) + λsin2θ = m2
Θ 𝜕𝜕θ 𝜕𝜕θ

or

d dy m2
[ (1 − x )
2 ] + (λ − )y=0 with x ∈ [-1, 1]
dx dx 1 − x2

This is a Sturm-Liouville eigenvalue problem.

For the special case of m = 0

d dy
[ (1 − x2) ]+λy=0
dx dx

Let y = ∑∞
𝑛𝑛=0 𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛 so y′ = ∑∞
𝑛𝑛=1 𝑛𝑛𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛−1
and y″ = ∑∞
𝑛𝑛=2 𝑛𝑛 𝑛𝑛 − 1 𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛−2

These variables are substituted into the above equation, and it gives a recursion relation

n(n+1) − λ
an+2 = a and a1 = 0
(n+2)(n+1) n

Based on the above two equations, a2n-1 = ….. = a3 = a1 = 0. Therefore, seting n = 0, 2, 4,….., one can
seek a serious solution. However, the power series solution does not converge for x = ± 1 unless choosing
λ = l (l+1) with l = 0, 1, 2,……. This yields the differential equation
The series must terminate with a finite number (n=l) of
d dy terms in order for our solution to have finite value. The
[ (1 − x2) ] + l (l+1) y = 0 or
dx dx best way to terminate the series is to equate the
numerator in the recursive equation with zero.
(1 − x2) y″ - 2xy′ + l (l+1) y = 0 n(n+1) − λ = 0 or λ=n(n+1) = l (l+1).

This is the Legendre differential equation whose solutions are Legendre polynomials denoted by Pl(x).
For the more general case of m ≠ 0

The equation with m ≠ 0 and λ = l (l+1) becomes

d dy m2
[ (1 − x )
2 ] + [ l (l+1) − ]y=0
dx dx 1 − x2

This is the Associated Legendre differential equation whose solutions are Associated Legendre
polynomials. The two linearly independent solutions are denoted by P𝑚𝑚 𝑚𝑚
𝑙𝑙 (x) and Q 𝑙𝑙 (x).

𝑚𝑚
y(x) = C1 P𝑚𝑚
𝑙𝑙 (x) + C2Q𝑙𝑙 (x)

However, Q𝑚𝑚
𝑙𝑙 (x) → ∞ at x = ± 1. Because wave function should be finite; therefore, C2 =0. So,

Θ(θ) = C1 P𝑚𝑚
𝑙𝑙 (cosθ)

In the table on next slide a few associated Legendre polynomials are listed.
Associated Legendre polynomials
1. The associated Legendre functions are related to the Legendre polynomials by
m
2 m/2 d
P𝑚𝑚
𝑙𝑙 (x) = (-1)m (1 - 𝑥𝑥 ) P (x) l = 0, 1, 2,……. and m = 0, 1, 2,…….
dxm l

2. P0𝑙𝑙 (x) = Pl (x)

3. Since the associated Legendre equation is the same for positive and negative m, P𝑙𝑙−𝑚𝑚 (x) = P𝑚𝑚
𝑙𝑙 (x)

m
d 𝑚𝑚
4. Since Pl (x) is a polynomial of degree l, then for m > l, m Pl (x) = 0 and P𝑙𝑙 (x) = 0. Therefore,
dx

l≥ 𝑚𝑚 or - l ≤ m ≤ l

8π2 I
5. λ= 2 εrot = l (l+1), the rotational energy εrot is dependent on l only.
h
The product of the angular dependence are called the Spherical Harmonics

𝑖𝑖mφ
Ψ(θ, φ) = Θ(θ)Φ(φ) = A P𝑚𝑚
𝑙𝑙 (cosθ) 𝑒𝑒

The coefficient A is determined with the normalization condition. The results are

Ψ(θ, φ) = (-1)m
(2𝑙𝑙+1)(𝑙𝑙−𝑚𝑚)!
P𝑚𝑚 𝑖𝑖mφ
4π (𝑙𝑙+𝑚𝑚)! 𝑙𝑙 (cosθ) 𝑒𝑒
 𝟐𝟐
Wave Function Ψ(θ, φ) (Spherical Harmonics) Plotted in 3-D
Space (for m > 0)
1. Solution exists only when l ≥ m .
2. Same solutions can be plotted for m < 0.

Iso-surface Contours
 2
h
Quantized rotational energy εrot = 2 l (l+1) and l ≥
8π I
𝑚𝑚

Degeneracy m
42 l =6
2
h
ε/( 2 )
8π I (All energy levels have degeneracy.)

30 l =5

g=2l+1 l, l-1, ..1, 0, -1, …- l-1, -l

20 l =4

12 l =3 g=7 3, 2, 1, 0, -1, -2, -3

6 l =2 g=5 2, 1, 0, -1, -1, -2

l : energy level 1, 0, -1
2 l =1 g=3
m : quantum number
0 l =0 g=1 0
Allowed rotational energies for CO
Vibrational Energy – Harmonic Oscillator
1. Linear vibrating motions of atoms due to the intermolecular forces.
2. Vibrational motion of diatomic molecules.
3. Vibration motion of atoms in a crystal lattice about their equilibrium positions.
4. Oscillators in the wall of the body that are in equilibrium with radiation of frequency υ.

The vibration of the atoms of a molecule may be modeled as a harmonic oscillator.

Let r represent the instantaneous distance

between the atoms.
Center
m2 of mass m1
r = re ± (r1 + r2) (1)

Since no external forces are involved,

r2 re r1 momentum is conserved.
r
m1 ṙ 1 = m2 ṙ 2 (2)
Eqn. (1) is differentiated to yield

̇ ṙ 1 + ṙ 2
𝑟𝑟=

The above equation is introduced to Eqn. (2).

m1 ṙ 1 = m2 (𝑟𝑟̇ - ṙ 1 ) = m2 𝑟𝑟̇ - m2 ṙ 1

m1 (m1 + m2 ) ṙ 1 = m1 m2 𝑟𝑟̇

m1 m2
m1 ṙ 1 = 𝑟𝑟̇
m1 + m2
m1 m2
m1 ṙ 1 = me 𝑟𝑟̇ where me = , reduced mass.
m1 + m2

In classical mechanics, the motion of an oscillating, elastic body is monitored by

me 𝑟𝑟̇ = - K r where K is the spring constant.

 K K
Solution: r = A sin t + B cos t
me me

Boundary conditions: At t = 0, r = ro
At t = 0, 𝑟𝑟̇ = 0

The resultant solution is

K
r = B cos t
me

Apparently, the frequency of oscillation is

1 K
υ = 2π m
e
 In quantum mechanics, the Schrödinger equation for harmonic oscillator is written as
2
d Ψ 8π2me
+ 2 (E − V) Ψ= 0 (E is vibrational energy including kinetic and potential energies.)
dr2 h
1
where potential energy V = K r2
2
2
d Ψ 8π2me 1
+ (E − K r2) Ψ= 0 or
dr2
h
2
2
2
dΨ
2 + (A − B r ) Ψ= 0
2
dr

2 8π2me 1 8π2me
Variables conversion: Let Ψ = 𝑒𝑒 −𝑥𝑥 /2 v(x), Br2 = x2, A= E, B = K , C =A/B.
h
2
2 h
2

v″ − 2xv′ + ( C − 1 ) v = 0

This is called the Hermite equation, whose solutions are Hermite polynomials.
Let v = ∑∞
𝑛𝑛=0 𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛 so v′ = ∑∞
𝑛𝑛=1 𝑛𝑛𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛−1 and v″ = ∑∞
𝑛𝑛=2 𝑛𝑛 𝑛𝑛 − 1 𝑎𝑎𝑛𝑛 𝑥𝑥
𝑛𝑛−2

The above equation becomes

∞ ∞ ∞
� 𝑛𝑛 𝑛𝑛 − 1 𝑎𝑎𝑛𝑛 𝑥𝑥 𝑛𝑛−2 − � 2𝑥𝑥𝑛𝑛𝑎𝑎𝑛𝑛 𝑥𝑥 𝑛𝑛−1 + (C – 1) � 𝑎𝑎𝑛𝑛 𝑥𝑥𝑛𝑛 = 0
𝑛𝑛=2 𝑛𝑛=1 𝑛𝑛=0
Shift
∞ Add one term ∞ ∞
� 𝑛𝑛 + 2 𝑛𝑛 + 2 − 1 𝑎𝑎𝑛𝑛+2 𝑥𝑥 𝑛𝑛 − � 2𝑛𝑛𝑛𝑛𝑛𝑛 𝑥𝑥 𝑛𝑛 + (C – 1) � 𝑎𝑎𝑛𝑛 𝑥𝑥𝑛𝑛 = 0
𝑛𝑛=0 𝑛𝑛=0 𝑛𝑛=0

∞
� 𝑛𝑛 + 2 𝑛𝑛 + 2 − 1 𝑎𝑎𝑛𝑛+2 + [− 2𝑛𝑛 + C – 1) 𝑎𝑎𝑛𝑛 𝑥𝑥 𝑛𝑛 = 0
𝑛𝑛=0

The coefficient for each power of x must equal zero:

𝑛𝑛 + 2 𝑛𝑛 + 2 − 1 𝑎𝑎𝑛𝑛+2 + [− 2𝑛𝑛 + C – 1) 𝑎𝑎𝑛𝑛 = 0

 𝑛𝑛 + 2 𝑛𝑛 + 2 − 1 𝑎𝑎𝑛𝑛+2 + [− 2𝑛𝑛 + C – 1) 𝑎𝑎𝑛𝑛 = 0

or

(2n + 1 ) − C
𝑎𝑎𝑛𝑛+2 = 𝑎𝑎
(n+2) (n+1) 𝑛𝑛

The series must terminate with a finite number of terms in order for our solution to have
any physical meaning. The best way to terminate the series is to equate the numerator in
the recursive equation with zero.
(2n + 1 ) − C = 0

So

C = 2n + 1
Note that

A 2E
C= = = 2n + 1 where E is the vibrational energy of interests.
B hυ

Therefore,

hυ
E= (2n + 1 ) n=0, 1, 2, 3, …….
2

n: vibrational quantum number

E: vibrational energy
Quantized vibrational energy E = h2υ (2n + 1 ) n=0, 1, 2, 3, …….

hυ
E/( )
2

9 n =4

7 n =3 (There is no degeneracy with the

vibrational energy levels in one-
dimensional problems. There is only
5 n =2 one energy state in each level.)

3 n =1
hυ
1 n =0
hυ/2
0

n : quantum number
Allowed vibrational energies for CO
Wave Functions

−𝑥𝑥 2 /2
Since Ψ = 𝑒𝑒 v(x) and v(x) is the Hermite polynomials, therefore the solution of the
Schrödinger equation which satisfy the normalization condition

∞
� Ψ𝑛𝑛 Ψ∗𝑛𝑛 𝑑𝑑𝑑𝑑 = 1
−∞

can then be given by

2𝜋𝜋2 𝑚𝑚𝑒𝑒 υ
4πmeυ 1/4 1 − 𝑥𝑥 2 meυ
Ψ𝑛𝑛 (x) = ( ) 𝑒𝑒 ℎ 𝐻𝐻𝑛𝑛 [(2π )x]
h 2𝑛𝑛 𝑛𝑛! h

where 𝐻𝐻𝑛𝑛 (x) is the Hermite polynomials.

Hermite Polynomials – The Eigenfunctions
 Ψ𝑛𝑛 (x)
n =6 13hυ/2
n =5
n =5 11hυ/2

n =4 9hυ/2

Classical oscillator
n =3 7hυ/2

n =2 5hυ/2

n =1 3hυ/2

n =0 hυ/2

x
Interpretation of 1-D Wave Function for Harmonic Oscillator

Classical oscillator
 Energy is Quantized

Energy
Continuous

Energy
Big things, small relative
energy spacings, energy
looks classical (i.e.,
continuous) Time

Energy
Energy
Quantized
Small things, large relative
energy spacings, must
consider the energy levels to
be quantized Time
 What energy transitions are possible?
Energy ε4—ε3, ε4—ε2, ε4—ε1

If these energy differences are:

2 x 10-19 J, 5 x 10-19 J, 9 x 10-19 J,
ε5
Respectively, what are the frequencies
ε4 of the emission lines that we should
see?

ε3 ε = hν so ν= ε/h where
(ν = frequency, h = 6.6 x 10-34 J·s)
For ε4—ε3,
ε2
ν = (2 x 10-19J) / (6.6 x 10-34 J·s)
= 0.3 x 1015 Hz
= 3.0 x 1014 Hz

ε1 Similarly,
ν = 7.5 x 1014 Hz (for ε4—ε2)
ν = 13.5 x 1014 Hz (for ε4—ε1)
 Not only can these atom only
Energy
EMIT photons of a certain
frequency, but they can only
ABSORB light of a certain
frequency.
ε5

ε4

ε3

ε2
Photon

ε1
 Quantum States and Degeneracy
The quantum states may be the
atomic orbitals.

3s

2s

1s The number of quantum states having the

same energy is called the degeneracy, gn.