Spectroscopy

The Schroedinger Equation

Stationary States

Nature of EM Radiation

Interaction of matter with EM radiation

Perturbation Theory

Selection Rules

Molecules and their energy levels

 Spectroscopy

Source of Photons
Molecule

GROUND
STATE

EXCITED!
EXCITED!

Molecule gets excited

only if the frequency
is right! + selection rules
Molecule and Light
- BOTH
Quantum objects!

Blistering Barnacles!
Quantum Mechanics

All particles have

a dual nature!
Special Solutions: Stationary States

Time Independent
Schrdinger Equation
 three dimensional
problem

Nuclear Electronic K.E Interaction

K.E
Electromagnetic Waves

7
These too, OK
8
>> size of the molecule
Magnetic moment
Molecule

EXCITED!

EXCITED!
New time dependent
Hamiltonian
What is the use? He
cannot solve even the
old one!
Eext/Eint =10-8
We need to solve

Small!
 Transition
moment integral

Energy
conservation
 Also,
h = E Induced Induced
Absorption Emission
n

2mn EXCITED!
Rm!n = () N m
30 ~ 2

2
mn Bmn
Rn!m = () N n
30 ~ 2
 Induced Induced
Absorption Emission

The two rate constants are EQUAL -

EXCITED!
Put the molecule into a cavity -
Populations have to become equal!
It will VIOLATE Boltzman distribution!

So there must be
SPONTANEOUS
Spontaneous
EMISSION
emission

Amn
EXCITED!
Excited States decay!

Except the
ground state!

EXCITED!
EXCITED!

Nothing lives for

ever! 21
Selection Rules

Light polarized in
X-direction:
Hydrogen emission spectrum

23
 (UV)

(Visible)

(IR)
Molecules
We will look at only
these two!
 Electronic
absorption in
UV-Vis region
 Vibrational
transitions in
IR region Electronic+

Vibrational

transitions

Vibrational transition
 Rotational
transitions in
Microwave

One can have purely rotational or,

vibrational+rotational
Electronic+vibrational+rotational
transitions Few cm-1
Microwave Spectroscopy
Wave length ~ 1 cm to 100 m
Wave number ~ 1 to 100 cm-1.

Frequency ~ 3 x 1010 to 3 x 1012 Hz

Energy ~ 10 to 1000 Joules/mole
 Spectrum of CO

Equally spaced
lines

3.84235 cm-1
Prof. E Arunans lab (IPC)
Rotation of a diatomic molecule

r2 r1

m2 m1
R
The Rigid Rotor

Two quantum numbers

J and M
 J
EJ
3 12B

(2J+1) fold 2 6B
degeneracy!
1 2B
0 0
Electric field + diatomic molecule
 Selection Rules
Must have a
permanent
Final Initial
dipole
state state
moment
Transition
Moment =
Integral
X -part

Y -part
 J EJ
3

Blue ALLOWED 2 6B
Red NOT
1 2B
0 0
 J EJ
3 12B

2 6B

Equally 1 2B
spaced
0 0
lines!

2B 4B 6B 8B
 Diatomics
HCl : B= 10.59 342 cm-1

Re = 1.275 Angstroms = 1.275 x 10-10meters =

127.5 picometers.

C O : B= 1.92118 cm-1
12 16
 Polyatomics

1. Linear Molecules
similar to
diatomics 16O12C32S - B = 6,081.48 MHz
16
O12C33S - B = 6,005.05 MHz
16
O12C34S - B = 5,932.83 MHz

(from: Graybeal)
 IR Spectroscopy
Wave length ~ 100 m to 1 m
Wave number ~ 100 to 10,000 cm-1

Frequency ~ 3 x 1012 to 3 x 1014 Hz

Energy ~ 1 kJ to 100 kJ /mole
 HCl absorptions
2885.9 cm-1 fundamental band strong
5668.1 cm-1 first overtone weak
8347.0 cm-1 second overtone
10923.1 cm-1 third overtone
13396.0 cm-1 fourth overtone
 Potential Energy Curve

V(r)

r
Harmonic Approximation
Vibration of a diatomic molecule

m1

m2

Centre of mass
does not move!
Quantum Mechanics of vibration
Electric field + vibrating diatomic molecule
Must haveSelection
an Rule
oscillating
dipole Initial
Final
moment state
state
Transition
Moment
Integral
 3

1
0
Blue ALLOWED
Red NOT
 3
2

0
Morse Potential
Triatomics

H2O
Symmetric stretch
Asymmetric stretch
Bending
CO2
Symmetric Stretching
Bending
Asymmetric Stretching
Fingerprinting Region