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Lecture 13: Raman Spectroscopy

Before going to Raman spectroscopy, we mention one point regarding


rotational and vibrational spectroscopy. The spectroscopy that we had de-
scribed were pure rotational and pure vibrational spectroscopy. It is also
possible to have a combination of both. We could have a vibrational spec-
trum where the rotational transitions are also observed. This is the case for
high resolution vibrational spectroscopy. In this case, a molecule in a vibra-
tional state v and rotational state J makes a transition such that v = 1.
The final state can have rotational state J + 1(called R branch) or J 1
called P branch of the spectrum. The Q branch corresponds to final state
with J = 0. This is forbidden for linear molecules. Though the analysis of
vibrational-rotational spectrum is not very complicated, we will not discuss
it in this course.
We have noticed that both IR and rotational spectroscopy cannot give
us information about homonuclear diatomic molecules. Raman Spectroscopy
is an alternative to absorption spectroscopy which can give us information
about homonuclear diatomic molecules. In Raman Spectroscopy, the inten-
sity of scattered light is detected as opposed to the intensity of transmitted
light. When light falls on a sample, a small part of it gets scattered in differ-
ent directions. By scattering, we mean that the molecules absorb the light
and emit light by going to a different state. The scattered light can have the
same frequency as the incident light, or it can have higher or lower frequency.
The Raman spectrum consists of lines due to these scattered light rays. The
scattered light with the same frequency is referred to as Rayleigh scattering.
The scattered light with lower frequency(energy) is referred to as Stokes lines
in the spectrum and that with higher frequency is referred to as anti-Stokes
lines in the spectrum.
Usually, only a small fraction (about 1 per million) of the incident light
is scattered, so we need a very sensitive technique for Raman scattering.
In addition, the frequency shifts are also very small as we shall see below,

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so nowadays, a laser light source is used. The original Raman effect was
discovered using focussed sunlight or mercury arc lamps. The discovery of
this effect led to C.V.Ramans Nobel prize in Physics in 1930. Raman spec-
troscopy is right now one of the most widely used methods of analysis of all
materials.
If the frequency of incident light is and that of scattered light is 0 , then
by energy conservation, we have

Ei + h = Ef + h 0

where Ei and Ef are the energies of the initial and final states of the molecule.
Thus, in scattering the light at a different frequency, the molecule goes from
an initial state to a final state. Now, we can write

h( 0 ) = h = hc = Ei Ef

Thus, the incident light frequency need not match the difference in energies,
but it is the difference between the frequencies of the incident and scattered
light that needs to match. Thus, any frequency of light can be used. Indeed
there is both Rotational and Vibrational Raman spectroscopy. In Rotational
Raman spectroscopy, the change in frequency of light is related to the dif-
ference in rotational energy levels. In vibrational Raman spectroscopy, this
change is related to the difference in vibrational energy levels.
Let us consider Rotational Raman spectroscopy. In this case, the con-
dition for observation of Raman spectrum is that the polarizability of the
molecule should change as the molecule rotates in an electric field. Thus
all molecules except a class of molecules called spherical rotors (e.g. CH4 ,
SF6 ) show Raman spectroscopy. For diatomic molecules, the specific selec-
tion rule is given by J = 0, 2. The J = 0 corresponds to Rayleigh line,
the J = 2 corresponds to the Stokes line and the J = 2 corresponds to
the Anti-Stokes line. When J = 2, the final state has a higher rotational
energy so the wavenumber of the scattered light is smaller. When J = 2,
the final state has lower rotational energy so the wavenumber of scattered
light is larger.
For the Stokes lines for the transition from J to J + 2, we have
Ei Ef
nu0 = nu+ = nu+B(J(J+1)(J+2)(J+3)) = nu4BJ6B = nu2B(2J+3)
hc
Thus the difference in wavenumbers corresponds to 6B, 10 B, 14B, ...

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For the Anti-Stokes lines for the transition from J + 2 to J, we have
exactly the same case, but now the wavenumber of the final state is higher.
The lines appear at wavenumbers 6B, 10 B, 14B, ...higher than the incident
wavenumber.
For vibrational Raman spectroscopy, the gross selection rule is that the
polarizability of the molecule should change as it vibrates. The specific selec-
tion rule for vibrational Raman spectroscopy is v = 1, where the v = 1
corresponds to Stokes lines and the v = 1 corresponds to Anti-Stokes
lines.