BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 5

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Summary (Lecture 4)
Simplest Application of Quantum Mechanics
to a Microscopic system

Translation Motion in 1-D & 2-Dimension Box:

Energy & Wavefunction
Orthogonality
Harmonic Oscillator: Wavefunction

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Vibrational motion: Quantum Mechanics

A wavefunction for a one-dimensional harmonic oscillator can be
represented by time-independent Schrdinger equation:

=E
2 d 2 1 2
kx E

2
2
2m d x

1/ 2

k

m

Wavefunction of Harmonic Oscillator:

Boundary conditions: x

4 2m

(derivation not in syllabus)

n N n H n x e

x 2

n 0,1,2,...
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Quantum Mechanical Harmonic Oscillator

Total Energy: Eigen value
2 d 2 1 2
kx E

2
2
2m d x

Schrdinger equation

Solving this
(derivation not in syllabus)
x 2
x 2
2 d 2 1 2
1

2
2

kx
N
H
x
e

[
n

]
N
H
x
e

n
n
n
n

2
2
m
d
x
2
2

Energy of the oscillator: En n h ; n 0,1,2,...

2

n vibrational quantum number

Force constant k
Particle mass m
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Quantum Mechanical Harmonic Oscillator

Total Energy: Eigen value
Energy of the oscillator:
1

En n h ; n 0,1,2,...
2

1
1
Ground state energy: E0 h
2
(Zero point energy: n = 0) 2
Atoms in a solid lattice or in polyatomic
molecules cannot have zero energy even at
absolute zero temperature. "zero point
vibration".

Evenly spaced energy levels.

Spacing h
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Quantum Mechanical Harmonic Oscillator

Wavefunction
Number of nodes is n.
Wavefunctions alternately symmetric or antisymmetric about x=0

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Quantum Mechanical Harmonic Oscillator

The Probability Distributions
As n increases, probability that the particle is in the
centre of the energy well decreases and the
probability of its being at the sides of the potential
well increases.
n becomes large, regions of highest probability
move towards the turning points:
Probability distribution resembles the classical
result. : Correspondence to classical mechanics.

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Example 3: Application of Quantum Mechanics

to particle moving on a circular path

Rotation in 2-D: particle on a ring

Angular
momentum: Lz (Jz) = pr

Particle constrained to move on a ring of radius r.

Entire energy is kinetic.
The potential energy is constant and can be taken
to be zero (as it is unchanged during rotation).
V = 0 (assumption)
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Particle on a ring: Quantum Mechanical aspect

Consider a particle of mass m moving in a circular path of radius

r (2-Dimension) such that it form an angle (with x-axis)
= KE + PE = p2/2m + 0

Lz = pr

2 d 2
d2
2 2 ( x, y) E ( x, y)

2m dx dy
.. Cartesian coordinates
The wavefunction may be better treated in terms of angle ()

( x, y)

( )

= p2/2m = Lz2/2mr2 = Lz2 /2I

2
2
L i

d
( )
z
E ( )
2
i Schrdinger equation 2 I
d

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Particle on a ring: Schrodinger Equation

2 d 2 ( )
E ( )
2
2I
d

.. Second order differential equation

Solve the Schrodinger equation and apply the boundary conditions

(derivation not in syllabus)

Wavefunction should be a periodically varying function

Cyclic Boundary conditions:

() = (2 + )
The wavelength should fit to the
circumference 2r of the circle.

m = 2r

m = 0, .
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Particle on a ring: Wavefunction

Wavefunction for particle on a ring:

m ( ) Ae im

(derivation not in syllabus)

Normalization
2

im
im
A
(
e
)
*
A
(
e
)d 1

im
im
A
(
e
)
A
(
e
)d 1

Normalized Wavefunction:

2
A
d 1

im

e
m ( )
1/ 2
2

1
A
2
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Particle on a ring: Energy

Schrdinger equation

2 2 ( ) 2 2 eim

1/ 2
2
2
2I

2 I 2
m 2 2

( )
2I

L2z m 2 2
Energy of particle on a ring: E

2I
2I

Energy levels
(Quantized)

m = 0, .
Degeneracy: All levels with ml 0 are doubly degenerate i.e., there
are two states of the same energy. The two states differ in the sense of
rotation.
No zero point energy. with ml = 0 ; Ground state nondegenerate.
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Particle on a ring: Wavefunctions

e 2i
2 ( )
2 1/ 2

e 1i
1 ( )
2 1/ 2

0 ( )

1/ 2

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Particle on a ring: Momentum Lz

Lz ml m 1 eim
i
i 2 1/ 2
l

1
iml
iml
e
ml ml
1/ 2
i 2
Angular momentum:

Quantized values of
angular momentum

ml

The solutions of the Schrdinger equation,

eigenfunctions of the Hamiltonian operator, are
also eigenfunctions of the angular momentum
operator Lz
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Example 4: Application of Quantum Mechanics

to particle on a Sphere (3-D Rigid Rotor)
z

Rotation in three dimensions

A particle could be considered as if moving on the surface of a sphere.
Rotational motion in three dimensions could be a mimic of
electrons around nuclei in atoms. (except that particle here is at fixed
distance r )
V=0
Two angles
(particle confined to a spherical space)
- the azimuthal angle
z
- the colatitude

x, y, z ,

Motion of a particle over sphere is like

motion of particle over a stack of rings, with
additional freedom to migrate between rings.

x
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Hamiltonian operator in polar coordinates

H
2 V
2m
2

2
2
2
2
2 ..
2
y
z
x
2

Cartesian coordina

2
2

1
1

2
2 2

sin

r
r

r
r
sin

sin

Since r is fixed

1
2
2
r

1
2
1

sin
..

2
2
sin

sin
18

polar coordinates

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