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SPECTROSCOPY- II
Raman spectroscopy - Polarisability of the molecule, Quantum theory of Raman effect,
Stokes and anti stokes lines, Raman shift, Rotation Raman and Vibration Raman spectra.
Basics of experimentation in Raman spectroscopy. Advantages of Raman Spectroscopy over
I.R. Spectroscopy.
Electron Spin Resonance - Introduction to electron spin resonance, instrumentation, the g-
value, hyperfine splitting with the examples of simple organic molecules.

RAMAN SPECTROSCOPY
When a beam of light is passed through a transparent medium (solid, liquid or gas) part of
the radiation gets scattered. Most of the scattered radiation is found to have the same
frequency as the incident radiation and it is called Rayleigh scattering.

Raman Effect:
Dr. C. V. Raman observed that when a monochromatic radiation is scattered by a
transparent medium, in addition to Rayleigh scattered radiation there exist scattered
radiations whose frequency is greater or smaller than that of incident radiation. This is
called Raman scattering or Raman Effect. Chandrasekhara Raman is credited with
discovering this effect in 1928.

Raman Shift:
The difference between the frequency of the incident radiation and that of scattered
radiation is called Raman Shift given by
 = i − s s = frequency of the scattered radiation
i = frequency of the incident radiation
Raman shift is a constant for a given substance i.e. it is characteristic of the substance
which produces the scattering and it is independent of the frequency of the monochromatic
radiation used.
Raman shift, 𝜈 is in the range of 100 – 3000 cm−1
The shifts in the frequency of the scattered radiation from the incident radiation are quite
small (about one photon in 104 in Rayleigh scattering and about one photon in 107 in the
case of Raman scattering) and hence the source must be very monochromatic for the shifts
to be observed. Moreover the intensity of the scattered radiation is low and so very intense
incident beams are needed. Thus Lasers have entirely replaced the mercury arc lamps used
originally.

Stokes and anti-Stokes lines: (Quantum theory of Raman Effect)

hi

Stokes Rayleigh Antistokes

Energy: hi > hs hi = hs hi < hs
Frequency: i > s  i = s i < s
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Rayleigh scattering:
Here the collision is elastic. The radiation with frequency i i.e. energy hi falls on the
molecule and it is scattered. The energy of the scattered radiation is the same as that of
incident radiation.
hi = hs These scattered lines have maximum intensity.
(Rayleigh scattering is responsible for the blue colour of the sky. Blue light scatters more
than other wavelengths because of its shorter wave length)

Stokes lines:
Here the incident radiation of energy hi collide with the molecules, give up some of its
energy to the molecules. The scattered radiation emerges with a lower frequency and hence
lower energy, hi  hs
These radiations are observed as lines to the lower frequency side of Rayleigh lines.

Antistokes lines:
When some of the photons of the incident radiation collide with molecules already in the
excited state, they may collect energy from the molecule and emerge as higher frequency
scattered radiation.
i.e. hi  hs These are called anti stokes lines and appear to the higher frequency
side of Rayleigh line.
Since very few molecules will be initially in an excited state probability of antistokes
transition is less and hence these lines have very low intensity compared to stokes.
For Stokes lines  = i − s is positive Raman Shift is +ve
For anti-Stokes lines  = i − s is negative Raman Shift is –ve
If the energy changes corresponding to Raman shift i.e. h is equal to the energy
difference of vibrational energy levels of molecules, we get Vibrational Raman spectra.
If the difference h is equal to the energy difference of rotational energy levels we get
Rotational Raman spectra.

Classical theory of Raman Effect: Molecular polarizability:

When a molecule is put in to a static electric field it suffers some distortion; the positively
charged nuclei being attracted towards the negative pole of the field and the electrons to the
positive pole. The separation of the charges causes an induced electric dipole moment to be
set up in the molecule and the molecule is said to be polarized.
The size of the induced dipole  depends both on the magnitude of applied field E and on the
ease with which the molecules can be distorted.
 =  E.
Here  is called the polarizability of the molecule and it depends on the ease with which the
electron shell of the molecule can be deformed.
We can represent polarizability in various directions most conveniently by drawing a
polarizability ellipsoid (squashed sphere). The axis of the ellipsoid is the least where the
polarizability is greater and vice versa (ellipsoid is the inverse of an electron cloud).
E.g. H – H Polarizability ellipsoid can be drawn as follows.

Anisotropic polarizability.
A molecule is said to have anisotropic polarizability if the induced dipole moment for a given
field is different in different directions. For example in H 2 molecule, the electrons forming
the bond are more easily displaced by the field along the bond axis than that across the
bond. All linear molecules have anisotropic polarizability. E.g. CO, HCl, CO 2, HC≡CH, H2 etc.
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Symmetric top molecules like CHCl3 have polarizability ellipsoid rather similar to linear
molecules. They have anisotropic polarizablity.
Spherical top molecules like CH4 have spherical polarizability that is they have isotropic
polarizablity.
In order for a molecular motion to be Raman active molecular polarizability,  must
change when that motion (either rotation or vibration) occurs. A change in the
polarizability is reflected by a change in either magnitude or direction of the polarizability
ellipsoid.

Pure rotational Raman spectra of linear molecules.

For a particular rotational motion to be Raman active the polarizability of the molecules
must change as the molecule rotates in the electric field of the incident radiation. For a
linear molecule rotating about the axis, polarizability will not change. Hence end over end
rotation need be considered.
Rotational energy levels for a linear molecule is given by
 J = B J (J + 1) cm−1
Transitions allowed between the rotational levels for Raman Scattering are given by the
selection rule J = 0, ± 2
(This is because during end over end rotation the ellipsoid presents the same appearance to
an observer twice in a 360° complete rotation)
J = 0 represents Rayleigh scattering.
Thus if the molecules gain rotational energy from the incident photon during collision a
series of lines to the lower frequency or wave number side (Stokes) is obtained.
When the molecules lose energy to the incident photon a series of lines to the higher
frequency side (anti-Stokes) is obtained.
The energy difference between the incoming and outgoing photons will be equal to the
energy difference in the quantized rotational energy levels (between which the transition is
allowed by the selection rule J = ±2)
The wave number of Raman spectral lines is given by J = J+2 − J cm−1
𝜈s = 𝜈i ± J = B(J +2)(J +3) − BJ(J +1) cm−1
𝜈Raman-rotation = 𝜈i ± B(4J + 6) cm−1 = B(4J + 6) cm−1

Negative sign indicates Stokes and plus sign indicates anti-Stokes.

By giving value J = 0, 1, 2, ….. we can see that the separation of the first line from the
exciting line is 6B cm−1, while the separation between the successive lines is 4B cm−1
When J = 0, 𝜈Raman = 𝜈i ± 6B
When J = 1, 𝜈 Raman = 𝜈i ± 10B
When J = 2, 𝜈 Raman = 𝜈i ± 14B

From the spectra, value of B can be obtained for a given molecule. From the value of B, bond
length can be calculated.
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Vibrational Raman spectra of molecules.

A molecule will be Raman vibration active if the molecular polarizability changes during a
particular vibration mode.
Selection rule for fundamental band of Raman vibration spectra is
v = 0 or ± 1; v = 0 corresponds to Rayleigh scattering
Energy absorbed or given during vibration is s = ωosc
v=0→v=1
𝜈s = 𝜈i ± s
𝜈s = 𝜈i ± ωosc cm−1
Where, ωosc is the fundamental oscillation frequency.
Negative sign indicates Stokes and plus sign indicates anti-Stokes lines.
The energy difference between the incoming and outgoing photons equals the energy
difference between the quantized vibrational energy levels.
Thus vibrational Raman spectra of a molecule will give a line on the lower frequency side of
i. i.e. Stokes line for each of the Raman active vibration. A weak mirror image on the higher
frequency side is the anti-Stokes line.
The separation of each line from exciting line gives the Raman active fundamental vibration
frequency ωosc of the molecule and hence the force constant ‘k’ can be calculated.

Raman Spectra as a compliment of IR spectra– Rule of mutual exclusion:

Statement:
For a molecule with a centre of symmetry the vibrations which are IR active are
Raman inactive and the vibrations which are IR inactive are Raman active.
This is called the rule of mutual exclusion or mutual exclusion principle.
Thus Symmetrical Stretching in CO2, Cl2, H2 etc. are IR inactive, hence Raman active.
If the molecule gives I.R as well as Raman lines for a particular mode of vibration then the
molecules can have no center of symmetry.
e.g i. CO2: Has center of symmetry because vibrations that is IR active
are Raman inactive and vice versa. Hence the structure is OCO
ii. N2O: Has no center of symmetry because it shows vibrational
modes which are both Raman and IR active. Hence the structure is NN–O
iii. H2O: All modes of vibration are Raman as well as IR active. There is no center of
symmetry. It is a bent molecule.
iv. BeCl2: Has center of symmetry because vibrations that are IR active are Raman
inactive and vice versa. Hence the structure is Cl–Be–Cl
v. CS2: Has center of symmetry because vibrations that are IR active are Raman inactive
and vice versa. Hence the structure is SCS
vi. HCN: All modes of vibration are Raman as well as IR active. There is no center of
symmetry. Hence the structure is H–C  N

Raman and IR activities of carbon dioxide and water

molecule Mode of vibration Raman IR

CO2 Symmetric stretch Active Inactive
Bending Inactive Active
asymmetric stretch Inactive Active
H 2O Symmetric stretch Active Active
Bending Active Active
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asymmetric stretch Active Active

Advantages of Raman over IR spectra (Vibrational spectra)

Raman spectra IR spectra

1. Observations are done in visible 1. Observations have to be done in
or U.V, hence conventional optics I.R range which involves complicated
and sample cells can be used instrumentation.
2.Homo nuclear diatomic molecules 2.Homo nuclear diatomic molecule
can be studied to obtain r0 and k do not give microwave or I.R spectra
3. Spectra can be taken using 3. Spectra cannot be taken using
water as a solvent because water is water as a solvent because water has
a weak Raman scatterer i.e. a strong IR absorption i.e. aqueous
aqueous solutions can be studied solutions cannot be studied
4.Ideal for studying weak vibrations 4. Difficult to study I.R spectra of
such as metal ligand stretching in complexes
Complex molecules
5. Very small quantities can be 5.Not easy to study very small
studied because the beam can be quantities
focused extremely finely.
6. Suited for study of large 6. Difficult to analyze large molecules
biological molecules.

Instrumentation
The invention of laser and its use as a source for Raman spectrometer revolutionized the
technique. Laser is ideal for Raman experiments as it gives a very narrow, highly
monochromatic, coherent beam, which can be focused very finely into a small sample. In
addition Laser can be extremely powerful and can provide intensities as great as one million
times that of sun light.
The following figure illustrates a typical Raman spectrometer.

The Laser beam (Helium – Neon Laser which emits radiation at 632.8 nm is commonly used)
is passed through the cell containing the sample.
The cell material must be transparent to the incident and scattered radiations. Because the
incident and scattered radiation often occur in the visible region, the cell can be constructed
from glass, quartz or silica. Often a glass capillary tube is used as a cell for liquid samples.
The light scattered sideways from the sample is collected and passed through a
monochromator (diffraction grating can be used, sometimes along with a lens or a prism) for
wave length selection.
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Next the radiation passes through the detector which is usually a sensitive photomultiplier
tube.
The signal after amplification is recorded. The recorder is usually a computer which plots
the Raman spectra.

Applications:
i. Raman spectroscopy is most often used for qualitative analysis in a manner analogous
to the use of IR spectroscopy. The recorded spectrum of the sample is compared with
the spectrum of known compounds or solutions. If a match between the sample
spectrum and a spectrum of known compound cannot be found, it is sometimes
possible to deduce the identity of the sample from correlation charts.
ii. The use of Raman spectroscopy often complements the use of IR, as Raman spectra is
due to change in the polarizability (which is induced by the incident radiation). The two
techniques do not necessarily detect the same vibrational levels. Thus Raman spectra
may provide information which might not be provided by IR
iii. Raman scattering can be used to qualitatively examine the surface of a sample by a
technique called molecular optical laser examination (MOLE). It has been used for
examining the defects in the industrial materials such as glasses, for environmental
analysis of dust particles, for examining biological samples, for study of semiconductors
and integrated circuits.

Numericals:
1. A sample was excited by the 4358 Å line of Hg. A Raman line was observed at 4447 Å.
Calculate the Raman shift in cm−1. At what wavelength in Å will the anti-Stokes line
appear in the Raman spectra?

i = 4358 Å = 4358 × 10−8 cm s = 4358 Å = 4358 × 10−8 cm

𝜈i = 1/ i = 1/ 4358 ×10−8 cm−1 𝜈s = 1/ i = 1/ 4358 ×10−8 cm−1
= 22950 cm −1 = 22480 cm−1
Raman shift Δ𝜈 = 22950 − 22480 = 470 cm−1
Since the Raman shift is +ve they are Stokes lines.

Anti-Stokes lines will appear at 𝜈i + Δ𝜈 = 22950 + 470 = 23410 cm−1

Raman anti-Stokes lines in terms of wave length  in Å = 1/𝜈 = (1/23410) cm
= (1/23410) ×108 Å
= 4272 Å

2. A sample was excited by the 632.8 nm radiation of a He-Ne laser and a Stokes line was
observed at 688.8 nm. Obtain the Raman frequency in cm−1. At what wavelength would
the corresponding anti-Stokes line appear in the Raman spectrum?
Answers: Raman frequency: 1,285 cm−1; anti-Stokes line: 585.2 nm.

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