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Raman Spectros

Raman spectroscopy involves irradiating a substance with monochromatic light and analyzing the scattered light. There are three types of scattered light - Rayleigh lines with the incident frequency, and Stokes and anti-Stokes lines with lower and higher frequencies, respectively. The difference in frequency between incident and scattered light is called the Raman shift. Raman scattering is explained by the formation of a short-lived complex between the molecule and photon during collision. Raman spectroscopy studies vibrational-rotational energy changes in molecules and is complementary to infrared spectroscopy.

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78 views3 pages

Raman Spectros

Raman spectroscopy involves irradiating a substance with monochromatic light and analyzing the scattered light. There are three types of scattered light - Rayleigh lines with the incident frequency, and Stokes and anti-Stokes lines with lower and higher frequencies, respectively. The difference in frequency between incident and scattered light is called the Raman shift. Raman scattering is explained by the formation of a short-lived complex between the molecule and photon during collision. Raman spectroscopy studies vibrational-rotational energy changes in molecules and is complementary to infrared spectroscopy.

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veluselvamani
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© © All Rights Reserved
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Raman Spectroscopy

When a substance (in any state) is irradiated with a monochromatic light of definite frequency (ν), the
light scattered (rpjwy;) at right angles (nrq;Fj;jhf) to the incident light.

The scattered light contains lines of

(i) incident frequency and

(ii) also of lower frequency

Sometimes lines of higher frequency are also obtained.

Thus, certain discrete (ntt;Ntwhd) frequencies above and below that of the incident beam will be
scattered. It is called Raman scattering.

The lines with lower frequency are called Stoke’s lines.

The lines with higher frequency are called Antistoke’s lines.

The line with the same frequency as that of the incident light is called Rayleigh line.

If νo is the frequency of the incident light and νR is the frequency of a particular scattered line, then:

∆𝜈 = 𝜈0 − 𝜈𝑅

This difference is called Raman frequency or Raman shift.

Theory of Raman spectra

When a beam of monochromatic light is passed through liquid or gas (scatterer), a small fraction of it is
scattered due to collisions between molecules of the scatterer and photons of light.

It is explained by assuming that a complex is formed between a molecule and a photon during very short
interval (~ 10-15 sec) of collision.

Two cases may arise depending upon whether a collision between a photon and a molecule in its ground
state is elastic or inelastic in nature.

Case 1

If the collision is elastic, the complex will dissociate to give the photon and molecule of the same energy.

This is equivalent to saying that the molecule merely deviates the photon without absorbing its energy.

This leads to the appearance of unmodified lines in the scattered beam and this is called Rayleigh
scattering.

Case 2
If the collision is inelastic, there will be exchange or transfer of energy between the scattering molecule
and the incident photon. Two different cases may arise here:

 A part of the energy of the incident light is used in exciting the molecule to the immediate
higher energy level and hence the radiation emitted by the molecule has lower energy than the
incident radiation. This results in the Stoke’s lines.
 On the other hand, some of the molecules which are already in an excited level, give their
excess energy to the incident radiation and move into the immediate lower energy level and
hence the radiation emitted by the molecule has higher energy than the incident radiation. This
results in the anti-Stoke’s lines.

Conditions for Raman spectroscopy

The Raman spectroscopy involves the study of vibrational-rotational energy changes in molecules by
means of scattering of light.

Raman spectra occurs as a result of oscillation of a dipole moment induced in a molecule.

If a molecule has a centre of symmetry, then the vibrations are centrosymmetric and are inactive in the
infra-red but are active in the Raman.

The vibrations which are not centrosymmetric are active in infra-red but inactive in Raman.

Mutual Exclusion principle

According to this principle, if a molecule has centre of symmetry (e.g., H2, CO2, C2H2 etc.), the Raman
active vibrations are infra-red inactive and vice-versa.

The molecule for which, centre of symmetry is absent can be IR as well as Raman active.

Consider the case of carbon disulphide (S=C=S). It is a centrosymmetric molecule. According to the rule
of mutual exclusion principle, all vibrations in it are Raman active and infra-red inactive.

In the case of nitrous oxide (N2O), the structure is N-N-O and not N-O-N. In this case, the vibrations are
simultaneously IR as well as Raman active. It shows that N2O has a linear structure and is not
centrosymmetric.

Infra-red and Raman spectra are complementary

For the infra-red spectrum to occur, the molecue must show a change in the dipole moment.

For the Raman spectra, there must be a change in polarisability of the molecule.

Infra-red and Raman spectra are complementary (epiwT cz;lhf;Ffpw) to each other because of the
following factors:

For all molecules with a centre of symmetry are active in Raman but inactive in IR.
Consider the linear molecule carbon dioxide, whose four fundamental modes of vibrations are:

Molecules for which centre of symmetry is absent, are both IR as well as Raman active.

Differences between Infra-red and Raman spectra

Infra-red spectra Raman spectra

1. It is due to absorption of a radiation by the 1. It is due to the scattering of radiation by


vibrating molecules. vibrating molecules.
2. The dipole moment of the molecule changes. 2. The polarisability of the molecule changes.

3. The intensity of IR absorption band depends 3. The intensity of the Raman line depends upon
upon the magnitude of the change in dipole the magnitude of the change of polarisability of
moment of the molecule. the molecule.
4. Water cannot be used as it is opaque to IR. 4. Water can be used as solvent.

5. Dilute solutions are generally used. 5. Concentrated solutions are used to increase the
intensity of Raman lines.
6. Optical systems are made up of special crystals 6. Optical systems are made up of glass or quartz.
like NaBr, CaF2, etc.

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