Chapter 18

A Quantum Mechanical Model for the Vibration

and Rotation of Molecules

Physical Chemistry 2nd Edition

Thomas Engel, Philip Reid

Objectives
Solving Schrdinger Equation
Introducing Angular Momentum
Introducing Spherical Harmonic
Functions

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Outline
1. Solving the Schrdinger Equation for the
Quantum Mechanical Harmonic
Oscillator
2. Solving the Schrdinger Equation for
Rotation in Two Dimensions
3. Solving the Schrdinger Equation for
Rotation in Three Dimensions
4. The Quantization of Angular Momentum
5. The Spherical Harmonic Functions
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.1 Solving the Schrdinger Equation for the Quantum

Mechanical
Harmonic Oscillator

Translational motion in various potentials

is described in the context of wave-particle
duality.
In applying quantum mechanics to
molecules, there are 2 motions for molecules
to undergo: vibration and rotation.
For vibration, the harmonic potential is
1 2
V x kx
2

where k = force constant

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.1 Solving the Schrdinger Equation for the Quantum

Mechanical
Harmonic Oscillator

The normalized wave functions are

1
x 2 / 2

2
x An H n x e
, and n 0,1,2,...

18.1 The Classical Harmonic

Oscillator

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Example 18.1
x 2

Show that the function

satisfies the
e
Schrdinger equation for the quantum
harmonic oscillator. What conditions does
this place on ? What is E?

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
We have
h 2 d 2 n ( x)

V x n x En n x
2
2 dx
2

x 2

h d e

2 dx 2

V x e h d 2xe 1 kx e
2
dx
2
x

x 2

x 2

h2
h2
1 2 x 2
x 2
2 2 x 2

2 xe

4 x e
kx e
2
2
2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
The function is an eigenfunction of the
total energy operator only if the last two
terms cancel:
H total e x

h 2 x 2
1 k
2

e
if

4 h2

Finally,
h2 h2
E

1 k h k

2
4h
2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.1 Solving the Schrdinger Equation for the Quantum

Mechanical
Harmonic Oscillator

Hermite polynomials states that

0 x

4

1 x

2 x

1/ 4

xe 1/ 2 x

1/ 4

1/ 4

1/ 4

3 x
9

e 1 / 2 x

2x
2x

1 e 1 / 2 x

3x e

1 / 2 x 2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.1 Solving the Schrdinger Equation for the Quantum

Mechanical
Harmonic Oscillator

The amplitude of the wave functions

approaches zero for large x values only
when
k
1
1
En h

n hv n with n 1,2,3,...

2
2

The frequency of oscillation is given by

v

1
2

18.2 Energy Levels and Eigenfunctions

for the Harmonic Oscillator

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Example 18.2
x 4 3 / 4 xe 1/ 2 x

a. Is
an eigenfunction of the
kinetic energy operator? Is it an
eigenfunction of the potential energy
operator?
b. What are the average values of the kinetic
and potential energies for a quantum
mechanical oscillator in this state?
1

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
a. Neither the potential energy operator
nor the kinetic energy operator commutes
with the total energy operator. Therefore,
x 4 / xe
because
is an eigenfunction of the
total energy operator, it is not an
eigenfunction of the potential or kinetic
energy operators.
3

1/ 2 x 2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
b. The fourth postulate states how the
average value of an observable can be
calculated. Because
then

2
2
h
d
E potential ( x) V ( x) and E kinetic ( x)
2 dx 2

E potential 1* ( x)V ( x) 1 ( x)dx

1/ 4

1 4
k
2

xe

1 / 2 x 2

1/ 2

4
dx k

1 2
kx
2

4 x
x
e

1/ 4

xe

(1 / 2 )x 2

dx

4 x
x
e dx

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
The limits can be changed as indicated in the
last integral because the integrand is an
even function of x. To obtain the solution, the
following standard integral is used:

1 3 5 2n 1
2 n x

dx

2 n 1 a n 1

The calculated values for the average

potential and
3 1/ 2
4 3
1 are
3k 3
k
kineticEenergy

h
potential

a 4 2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
Thus

Ekinetic

h d2
1 x dx
x
2
2 dx

4 3

*
1

1/ 4

xe 1/ 2 x

h 2 4 3

1/ 2

h 4

1/ 2

h2 d 2

2
2 dx

4 3

1/ 4

xe 1/ 2 x dx
2

x 4 3x 2 e x dx

h 4 3

2
2

x 3x e

4 2

x 2 dx

1/ 2

3 h 2 3
k

h
4
4

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
In general, we find that for the nth state,
Ekinetic ,n E potential ,n

h k
1
n

2
2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.1 Solving the Schrdinger Equation for the Quantum

Mechanical
Harmonic Oscillator

18.3 Probability of Finding the

Oscillator in the Classically Forbidden
Region

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.2 Solving the Schrdinger Equation for Rotation in

Two
Dimensions

Consider rotation, the total energy

operator can be written as a sum of
individual operators for the molecule:
H total H trans rcm H vib int ernal H rot cm , cm

Also the system wave function is a

product of the eigenfunctions for the
three degrees of freedom:
total trans rcm vib int ernal rot cm , cm

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Example 18.3
The bond length for H19F is 91.68 10-12
m. Where does the axis of rotation
intersect the molecular axis?

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Solution
If xH and xF are the distances from the axis of
rotation to the H and F atoms, respectively,
12
x

91
.
68

10
F
we canH write
and
xHmH=xFmF. Substituting mF=19.00 amu and
mH=1.008 amu, we find that xF=4.5810-12
m and
xH=87.10 10-12 m. The axis of rotation is
very close to the F atom. This is even more
pronounced for HI or HCl.
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.2 Solving the Schrdinger Equation for Rotation in

Two
Dimensions

The eigenfunction

the angle .

depends only on

A e iml and A e iml

The solutions above correspond to

clockwise and counterclockwise rotation.

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

Example 18.4
A
Determine the normalization constant

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

in

Solution
The variable can take on values between 0
and 2. The following result is obtained:
2

ml ml d 1
0

A e
2

iml iml

d A

d 1
0

1
A
2

Convince yourself that A

value.

has the same

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.2 Solving the Schrdinger Equation for Rotation in

Two
Dimensions

The energy-level spectrum is discrete and

is given by
h 2 ml2 h 2 ml2
Eml

for ml 0,1,2,3..
2
2 r0
2l

where ml = quantum number

We say that the energy levels with

are twofold degenerate.

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.2 Solving the Schrdinger Equation for Rotation in

Two
Dimensions

For rotation in the x-y plane, the angular

momentum vector lies on the z axis.
The angular momentum operator in these
coordinates takes the simple form
iz ih
Applying this operator
to an eigenfunction,

iml
ml h iml

ih
de
l

e ml h
z

2 d
2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.3 Solving the Schrdinger Equation for Rotation in

Three
Dimensions

For molecule rotating in two dimensions:

A eiml and A e iml , for ml 0,1,2,3,...

To make sure Y(,) are single-valued

functions and amplitude remains finite,
the following conditions must be met.
l l 1 , for l 0,1,2,3,... and
ml l , l 1 , l 2 ,...,0,..., l 2 , l 1 , l

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.3 Solving the Schrdinger Equation for Rotation in

Three
Dimensions

Both l and ml must be integers and the

spherical harmonic functions are written
in the form
Y , Yl ml , lml ml

The quantum number l is associated with

the total energy observable,
h2
El
l l 1 , for l 0,1,2,3,...
2I

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.4 The Quantization of Angular Momentum

The spherical harmonic functions,

are eigenfunctions of the total energy
operator for a molecule that rotates freely
in three dimensions.
l 2
The eigenvalue equation for the operator
can be written as
l 2Yl ml , h 2l l 1Yl ml ,

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.4 The Quantization of Angular

Momentum

The operatorslx , ly and lz have the following

form in Cartesian coordinates:


lx ih y z
y
x

ly ih z x
z
x


lz ih x y
x
y

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.4 The Quantization of Angular

Momentum

The operators have the following form in

spherical coordinates:
l ih sin cot cos
x

l ih cos cot sin

y

l ih
z

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.4 The Quantization of Angular

Momentum

For the operators in Cartesian

coordinates, the commutators relating the
operators
are given by

l , l ihl
l , l ihl
l , l ihl

Thus the spherical harmonics is as

l Y ml , ih
z l

for ml 0,1,2,3,...,l

1 iml
e
ml h ,
2

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.5 The Spherical Harmonic Functions

For spherical harmonic functions, these

are the first few values of l and ml:
1
4 1/ 2

Y00 ,

3
Y ,

1/ 2

cos

0
1

5
Y ,

16
1
1

5
Y ,

3 cos

1/ 2

1
2

15
Y ,

32

1
2

sin e i
1/ 2

5
Y ,

16
0
2

1/ 2

sin cos e i
1/ 2

sin 2 e i

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.5 The Spherical Harmonic Functions

The functions which form an orthonormal

set are given in the following equations:

1 1
3
1
px
Y1 Y1
sin cos
4
2

1
3
py
Y11 Y11
sin sin
4
2i
p z Y10

3
cos
4

d z 2 Y10

3 cos 2 1
16

d xz

1 1
Y2 Y21 415 sin cos cos
2

d yz

1
Y21 Y21 415 sin cos sin
2i

d x2 y2
d xy

1
Y22 Y22 a156 sin 2 cos 2
2i

1
Y22 Y22 1615 sin 2 sin 2
2i

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd

18.5 The Spherical Harmonic Functions

3D perspective plots of the p and d
linear combinations of the spherical
harmonics.

Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd