Professional Documents
Culture Documents
Ug Spectroscopy 2017 1
Ug Spectroscopy 2017 1
Stationary States
Nature of EM Radiation
Perturbation Theory
Selection Rules
Source of Photons
Molecule
GROUND
STATE
EXCITED!
EXCITED!
Blistering Barnacles!
Quantum Mechanics
Time Independent
Schrdinger Equation
three dimensional
problem
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
So there must be
SPONTANEOUS
Spontaneous
EMISSION
emission
Amn
EXCITED!
Excited States decay!
Except the
ground state!
EXCITED!
EXCITED!
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
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
(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
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
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