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Raman spectroscopy is a phenomenon of inelastic scattering of light which first postulated by Smekal in 1923 and first observed experimentally

in 1928 by Raman and Krishnan. Vibrational and rotational transition can be explored by examining the frequencies present in the radiation scattered by molecules in Raman Spectroscopy. Two types of scattering are readily identified. The most intense form of scattering, Rayleigh scattering (component of radiation scattered without change of frequency), occurs when the electron cloud relaxes without any nuclear movement. This is essentially an elastic process and there is no appreciable change in energy. Raman scattering on the other hand is a much rarer event which involves only one in 106-108 of the photons scattered. This occurs when the light and the electrons interact and the nuclei begin to move at the same time. Since the nuclei are much heavier than the electrons, there is an appreciable change in energy of the molecule to either lower or higher energy depending on whether the process starts with a molecule in the ground state (Stokes scattering) or from the molecule in a vibrationally excited state (anti- stokes scattering). Most molecules at rest prior to interaction with the laser and at room temperature are likely to be in the ground vibrational state. Therefore the majority of Raman scattering will be Stokes Raman scattering. The ratio of the intensities of the Stokes and anti-Stokes scattering is dependent on the number of molecules in the ground and excited vibrational levels. This can be calculated from the Boltzmann equation.

The gross selection rule for rotational Raman transitions is that the molecule must be anisotropically polarizable. The gross selection rule for vibrational Raman transitions is that the polarizability should change as the molecule vibrates. Raman scattering arises from a change in polarizability in the molecule. This means that symmetric vibrations will give the most intense Raman scattering. This is in complete contrast to infrared absorption where a dipole change in the molecule gives intensity and, at a very simple level, this means asymmetric rather than symmetric rather than symmetric vibrations will be intense. One crucial result which arises from this analysis is that irrespective of other symmetry considerations, for a centrosymmetric molecule, only vibrations which are g in character can be Raman active and only vibrations which are u in character can be infrared active. This is because irrespective of the exact irreducible representation, the g and u labels can be multiplied out and the final product must contain the totally symmetric representation and hence g. The rules are g x g=g, u x u=g and g x u=u. Since the Raman operators are g in character and the ground state is g, the excited state must be g if the vibration is to be allowed. In contrast, the infrared operator is u in character and so the excited state must be u if the vibration is to be allowed. Thus in a molecule with a centre of symmetry, vibrations

which are Raman active will not be infrared active and vibrations which are infrared active will not be Raman active. Note that, the symmetric vibrations (g) which are Raman active, and the asymmetric vibrations (u) which are infrared active. This analysis leads to a rule known as the mutual exclusion rule, which states that any vibration in a molecule containing a centre of symmetry can be either Raman or infrared active, but not both. In molecules without a centre of symmetry, there is no such specific rule. Nonetheless, in general, symmetric vibrations are more intense in Raman scattering and asymmetric vibrations in infrared scattering. Comparisons between Raman and Infrared spectroscopy, Raman spectroscopy is scattering spectroscopy which are involves the carbon allotropes and polarizable bond: C-C, C=C. Scattering involves a momentary distortion of the electrons distributed around a molecular bond. Thus, the molecule is temporarily polarized (a momentarily induced dipole that disappears upon relaxation and reemission. Infrared spectroscopy is absorption spectroscopy, which are involves the functional groups and polar bonds: C=O, O-H. It requires the vibrational mode of the molecule to have a change in the dipole moment or charge distribution associated with it. Only then, a radiation of same frequency interacts with the molecule, and promotes it to the excited state. To be visible in Raman vibration must change the polarizability of the molecule. Whereas, to be visible in Infrared vibration, must change the dipole moment of the molecule. An important advantage of Raman spectra over infrared lies in the fact that water does not cause interference; indeed, Raman spectra can be obtained from aqueous solution. Furthermore, glass or quartz cells can be employed, thus avoiding the inconvenience of working with sodium chloride or other atmospherically unstable confinements. Thus aqueous solutions can be studied by Raman spectroscopy but not by Infrared. For frequency range, Raman is from 4000- 50 cm-1 while Infrared from 4000700cm -1. Raman instrumentation was developed (based around arc lamps and photographic plates) and soon became very popular up until the 1950's.Since these early days, Raman instrumentation has evolved markedly. Modern instrumentation typically consists of a laser, sample illumination system, wavelength selector (Rayleigh filter), and a detector (typically a CCD or ICCD). Raman spectroscopy is essentially emission spectroscopy, and the bulk of the instrumentation is simply a typical visible-region spectrometer; the distinguishing characteristic of Raman work, of course, is the exciting source. The advent of accessible and relatively inexpensive laser sources during the past few years has caused a minor revolution in Raman techniques, by largely displacing the traditional mercury discharge lamp as an exciting source. Formerly the process of obtaining a good Raman spectrum of anything but the most straightforward samples involved as much art as science, required 10-20 ml of sample, and was often a very time-consuming operation; now Raman

spectra of virtually all samples can be run on a completely routine basis using one milliliter or less of sample and taking a few minutes only. In fact the laser is almost ideal as a Raman source; it gives a very narrow, highly monochromatic beam of radiation, which may be focused very finely into a small sample, and which packs a relatively large power. In conventional Raman experiments the sample is illuminated by monochromatic light. The registration of low intensity Raman scattering in the presence of strong Tyndall and Rayleigh scattering implies special requirements for Raman spectrometers. A Raman spectrometer has to combine very good filter characteristics for eliminating Rayleigh and Tyndall scattering with high sensitivity for detecting very weak Raman bands. There are three types of Raman instruments which are currently available; those are Raman grating spectrometer with single channel detector, FT- Raman spectrometer with near infrared excitation, and Raman grating polychromator with multichannel detector. Raman signal is normally quite weak and people are constantly improving Raman spectroscopy techniques. Many different ways of sample preparation, sample illumination or scattered light detection were invented to enhance intensity of Raman signal, stimulated raman, where the sample was irradiated with a very strong laser pulse. CARS (Coherent Anti-Stokes Raman), two very strong collinear lasers irradiate a sample. Resonance Raman, the Resonance Raman Effect takes place when the excitation laser frequency is chosen in a way that it crosses frequencies of electronic excited states and resonates with them. The classical theory of the Raman Effect, although not adequate, is worth consideration since it leads to an understanding of a concept basic to this form of spectroscopy is the polarizability of a molecule. When a molecule is put into a static electric field it suffers some distortion, the positively charged nuclei being attracted towards the negative pole of the field, the electrons to the positive pole. This separation of charge centers 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 the applied field, E, and on the ease with which the molecule can be distorted. Quantum theory of Raman Effect, as a stream of photons collides with a particular molecule the photons will be deflected without change in energy if collisions are perfectly elastic. If energy is exchanged between photon and molecule, the collision is said to be inelastic. The molecule can gain or lose discrete amounts of energy in accordance with quantal laws; the energy must coincide with a transition between two molecular energy levels.