Molecular Spectroscopy

The Diatomic Rigid Rotator

General Aspects of Molecular Spectroscopy




The rigid diatomic Molecule
m
1
m
2
r
1
r
2
C
m
1
r
1
m
2
r
2
=
r
0
THE MOMENT OF INERTIA IS I = r
0
2

Reduced mass
Rotational Energy Level
E
J
= h
2

In terms of wavenumber

J

=

E
J
/hc cm
-1


J

= BJ(J+1), where B = h
2
cm
-1


B is called as the rotational constant.
8
2
I
J (J+1) joules, where J = 0, 1, 2,..
8
2
I c
Intensities of Spectral Lines
Intensities depends on number of molecules
in a particular energy level Boltzmann
Distribution
N
J
/N
O
= EXP (-E
J
/kT) = EXP(-Bhc J(J+1)/ kT)

N
J
/N
O
0.98

There are as many molecules in the J=1 state, at
equilibrium as in the J=0, at T=300K (room temperature).
Further, there is more rapid decrease of N
J
/N
O
with
increasing J and with larger B.
J
E
X
P
(
-
B
h
c

J
(
J
+
1
)
/

k
T
)

1
10
0
B = 10 cm
-1
B = 5 cm
-1
Degeneracy of the energy states
The energy and angular momentum of a rigid
rotator are
E = I
2

P = I
P = (2EI)
1/2
= [J(J+1)]
1/2
units

eg., for J=1, P=(2)
1/2

11
Spacing between adjacent rotational levels j and j-1,
12
Rotational Spectroscopy
(1) Bohr postulate
/ h hc c v A = =
(2) Selection Rule
1
1 ( )
1 ( )
j
j absorption
j emission
A =
A = +
A =
Isotopic Shift
12
CO
13
CO
J
6
5
4
3
2
1
TYPICALLY ROTATIONAL SPECTRUM SHOWS
LINES CORRESPONDING TO 1-100 cm
-1
The Vibrating Diatomic Molecule (eg., HCl)
Cl
Cl
r
eq
H
H
H
H
BOND LENGTH
APPROX.
POTENTIAL
REAL/ EFFECTIVE
POTENTIAL
Morse Potential
THE PARAMETERS
E = k (r r
eq
)


osc
= 1/2 (k/)
1/2
Hz
osc
=
osc
/c cm
-1


Allowed vibrational Energies
E

= ( + 1/2)
osc

Selection rule : = 1
Vibrations in Rigid rotator !!
r
eq
= 0
1
2
3
E
N
E
R
G
Y

N
1
/N
O
0.008

The molecular population
Dies of very fast

Ignore all possible
Vibrational states
21
Vibrational Spectroscopy
Vibrational selection rule
1
1 ( )
1 ( )
absorption
emission
u
u
u
A =
A = +
A =
J = -1 P
J = +1 R
J = +2 S
J = -2 O
J = 0 Q

26
Vibration-Rotation Spectra
Infrared spectrum
J = 1
Raman spectrum
J = 0 , 2
27
Vibration-Rotation Infrared Spectrum of HCl

vib
is different for
H
35
Cl and H
37
Cl
molecules due to
the slight
difference in their
reduced masses.

au

au
972 . 0
36
35
Cl H
35
= =
974 . 0
38
35
Cl H
37
= =
28
Vibration-Rotation Infrared Spectrum of HCl
The lines due to
H
35
Cl transitions
are more intense
because the
isotopic
abundance ration
of H
35
Cl to H
37
Cl
molecules is 3:1.
29
Vibration-Rotation Infrared Spectrum of HCl

B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 4
Band center
H
35
Cl
Band center
H
37
Cl
30
Vibration-Rotation Infrared Spectrum of HCl
The rotational constant B slightly decreases as
going to higher vibrational levels. This results in
decrease of the gaps between transition lines as
one goes to higher frequencies.
B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 4
31
Vibration-Rotation Infrared Spectrum of HCl
The rotational constant B slightly decreases as going to higher
vibrational levels. This results in decrease of the gaps between
transition lines as one goes to higher frequencies.
32
Vibration-Rotation Infrared Spectrum of HCl
B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 2 B 4
Approximation of B
values
RAMAN SPECTROSCOPY
Nobel in 1930

Discovery of Raman Effect (Raman
Scattering)

(7 November 1888 21 November 1970)
WHAT IS RAMAN SPECTROSCOPY ?

Raman spectroscopy is the measurement of the
wavelength and Intensity inelastically scattered light
from molecules.

May be used to understand chemical
composition and molecular structure.

Used in CMP and chemistry to understand the
vibrational, rotational and other low-frequency
modes of a system.

Scattering
In addition to being absorbed and emitted by
atoms and molecules, photons may also be
scattered (approx. 1 in 10
7
in a transparent
medium). This is a molecular effect, which
provides another way to study energy levels.
ELASTIC INELASTIC
SYSTEM REMAINS IN
THE SAME
QUANTUM STATE
Resulting in CHANGE
IN THE QUANTUM
STATE
Scattering

in
=
out

Rayleigh scattering
E
in
= E
out
= h




in

out
Raman scattering
E
in
E
out


VIRTUAL STATES
EXCITED STATES
GROUND STATE
RAMAN SCATTERING SELECTION RULES
RAMAN SCATTERING SELECTION RULES
Rotational Raman
Some fine points
Inelastic scattering can be in analogy with a ball
bearing hitting a drum so that it starts to oscillate at
its natural frequency. Similarly if the drum is already
oscillating and the ball bearing hits it at the right
phase, it may get reflected at a higher energy.
In order to be Raman active, a molecular rotation or
vibration must cause some change in the component
of molecular polarizibility.
Strokes lines (those scattered with a lower frequency
than the incident radiation) are generally more
intense than the anti-stroke lines, because the
former is accompanied by an increase in molecular
energy.
IR
RAMAN
Why is Raman Different to IR?
Selection rules are therefore different and can be
exclusive for centrosymmetric molecules

IR
IR
-
-
Change in Dipole Moment
Change in Dipole Moment
Raman
Raman
-
-
Change in
Change in
Polarizability
Polarizability
M M - -
M M - -
M M + +
M M + +
M M - -
M M - -
M M + +
M M - -
M M - -
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _ + +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _
+ +
_ _ + +
_ _
+ +
_ _
+ +
_ _
+ +
_ _