Section 6

Raman Scattering
(lecture 10)
Quantum theory
of atoms / molecules
Previously:
Quantum
Mechanics
Valence
Atomic and Molecular Spectroscopy
Raman Scattering
The scattering process
Elastic (Rayleigh) and inelastic (Raman) scattering
Selection rules for Raman
Similarities and differences with dipole allowed absorption
6.1 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 not due to defects or
dust but a molecular effect which provides another way to study energy levels.
This scattering may be:
Elastic and leave the molecule in the same
state (Rayleigh Scattering) or
Inelastic and leave the molecule in a different
quantum state (Raman Scattering)
6.2 Rayleigh Scattering
Lord Rayleigh calculated that a dipole scatterer << l scatters with an intensity:
( )
2
2
0 4 2
t o
u

= +
polarizability no. of scatterers
distance
scatterer - observer
wavelength
4

5 times more effective

for 400nm than 600nm
Hence the sky is blue!
(and sunsets red)
n.b.,
Nobel Prize 1904
(physics)
Nobel Prize 1930
(physics)
6.3 Inelastic (Raman) Scattering
Energy exchange between the photon and molecule leads to inelastic scatter.
n
0
n
t
In Raman Scattering the scattered photon has
different energy (frequency, wavelength) than the
incident photon:
Stokes lines are those in which the photon has
lost energy to the molecule
Anti-Stokes lines are those in which the photon
has gained energy from the molecule
n
0
+ n
t
The strongest scattering is Rayleigh scatter
S
t
o
k
e
s
A
n
t
i
-
S
t
o
k
e
s
R
a
y
l
e
i
g
h
n
0
+ n
t
n
0
v
n
0
n
t
n
0
Since molecular energy levels are quantised this
produces discrete lines from which we can gain info
on the molecule itself.
Virtual state
6.4 Raman Scattering selection rules
Scattering is not an oscillating dipole phenomenon! (no TDM)
ind
u o =
The presence of an electric field E induces a
polarization in an atom/ molecule given by
polarizability
If the field is oscillating (e.g., photon)
( )
0 ind
u o tv =
In atoms the polarizability is isotropic, and the atom acts like an antenna and re-
radiates at the incident frequency Rayleigh Scattering only
In molecules the polarizability may be anisotropic, and depends on the rotational
and vibrational coordinates. This can also give rise to Raman Scattering.
Gross Selection Rule:
To be Raman active a molecule must have anisotropic polarizability
[Less restrictive than the need for a dipole moment, symmetric molecules can be Raman active]
6.5 Rotational Raman
6.5.1 Linear Molecules: The polarizability tensor is anisotropic (o

= o
||
)
As a molecule rotates the polarizability presented to the E field changes:
the induced dipole is modulated by rotation
results in rotational transitions
S
t
o
k
e
s
A
n
t
i
-
S
t
o
k
e
s
R
a
y
l
e
i
g
h
n
0
J
J + 2
J 2
Effective two-photon process and
Specific Selection Rule:
A = J
Rayleigh
Stokes lines
Anti-Stokes lines
Even non-polar molecules (O
2
, N
2
, CO
2
) exhibit rotational Raman Spectra
6.5.1 Rotational Raman spectra
A = J
Assuming a rigid rotor: F(J) = BJ(J+1)
Stokes lines are observed at:
( ) ( ) { } ( )
0 0
v v v = + = + J J J
and Anti- Stokes lines at:
( ) ( ) { } ( )
0 0
v v v = + = + J J J - 2
i.e.,
a gap of 6B between n
0
and 1
st
lines of
each branch
lines in each branch of equal spacing = 4B
n.b. 1
st
Anti-Stokes line is J = 2
6.5.1 Example Rotational Raman spectra
H
2
Stokes
Anti-Stokes
3:1 intensity alternation observed due to
nuclear spin-statistics (3 times as many
ortho-H
2
levels (odd J) as para-H
2
(even J))
Spectrum allowed because all transitions
connect levels of the same symmetry.
For the same reason, alternate lies are completely missing in the Raman spectra of
16
O
2
and C
16
O
2
.(if the level doesnt exist one cant see transitions to and from it)
Likewise the
14
N
2
Raman spectrum shows 2:1 aternations
In deducing B from spacings, beware the possibility of missing lines in the spectrum.
6.6 Vibrational Raman
Gross Selection Rule: The polarizability must change during the vibration
Even homonuclear diatomics satisfy the gross selection rule and exhibit Raman spectra
Specific Selection Rule: Dv = 1 (+ Stokes, Anti-Stokes)
n.b. Anti-Stokes rarely observed because v > 0 weakly populated
6.6.1 Diatomics:
6.6.2 Polyatomics:
Need to check each normal mode against the
gross selection rule:
Raman
Active
Raman
Active
Raman
Active
H
2
O
0 q
o
=
| |
=
|
\ .
In practice this means the normal mode must transform with the same symmetry as
the quadratic forms (x
2
, xy, etc.)
CO
2
: D
h
Raman
Active
Raman
Inactive
Raman
Inactive
IR
Active
IR
Active
IR
Inactive
g
+
E
u
+
E
u
H
6.7 The Rule of Mutual Exclusion
In the case of CO
2
it is not coincidence that those modes which are Raman active are
IR inactive and vice versa. This is an example of the rule of mutual exclusion which
states:
In a centrosymmetric molecule (i.e., one with a centre of inversion symmetry)
a vibrational mode may be either IR active or Raman active but not both.
acetylene
D
h
Raman Raman Infra Red
Infra Red Raman
6.8 Vibration-Rotation Raman
In the same way that rotational transitions accompany vibrational absorptions so
rotational structure is observed in high resolution Raman spectra.
Vibrational / Rotational Raman
spectrum of CO.
The Q-branch identifies the
vibrational spacing (w
e
-2w
e
x
e
)