The Raman Spectra

OPUS differentiates between the Raman spectrum and the single channel spectrum. The single channel spectrum of the Stokes and anti-Stokes Raman scattering for a sulphur sample is shown in Fig. 4.4. Note that the abscissa here is expressed in absolute wavenumbers. Therefore, the exciting laser line appears at vl = 9394 cm and the bands at wavenumbers lower and higher than 9394 cm arise from Stokes and anti-Stokes Raman scattering, respectively. On the other hand, a standard Raman spectrum comprises the spectral range from 0 to 3500 cm. Load the file RAMAN SULPHUR and find out the difference between these two types of spectra. 

The intensity of Raman scattering is proportional to the square of the change in the molecular polarizability a resulting from a normal mode q  

Otherwise stated, a vibrational mode that satisfies the requirement da 

One should be aware of the fact that Raman spectroscopy is a complementary technique to IR spectroscopy. In cases where a chemical compound exhibits a centre of symmetry, certain normal vibrations will be only Raman active and certain normal vibrations will be only IR active. Thus, one needs both techniques to 

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This spectrum is called a Raman spectrum and corresponds to the vibrational or rotational changes in the molecule. The selection rules for Raman activity are different from those for i.r. activity and the two types of spectroscopy are complementary in the study of molecular structure. Modern Raman spectrometers use lasers for excitation. In the resonance Raman effect excitation at a frequency corresponding to electronic absorption causes great enhancement of the Raman spectrum. 

Because of the two frequencies, Wj and Wg, that enter into the Raman spectrum, Raman spectroscopy may be thought of as a two-dimensional fomi of spectroscopy. Nomially, one fixes oij and looks at the intensity as a frmction of tOj, however, one may vary tOj and probe the intensity as a frmction of tOj - tOg. This is called a Raman excitation profile. 

The resolution of the Raman spectrum is detemiined by the monoclnomator. Furthennore, since the light bemg measured is in the visible region, usually around 20 000 cnc the resolution of the monoclnomator must be significantly better than that of its IR counterpart because the resolving power is described by Av/v. That is, for... 

It was first reported in 1974 that the Raman spectrum of pyridine is enhanced by many orders of magnitude when... 

Carey D M and Korenowski G M 1998 Measurement of the Raman spectrum of liquid water J. Chem. Phys. 108 2669-75... 

The Raman spectrum of nitric acid shows two weak bands at 1050 and 1400 cm. By comparison with the spectra of isolated nitronium salts ( 2.3.1), these bonds were attributed to the nitrate and nitronium ion respectively. Solutions of dinitrogen pentoxide in nitric acid show these bands , but not those characteristic of the covalent anhydride , indicating that the self-dehydration of nitric acid does not lead to molecular dinitrogen pentoxide. Later work on the Raman spectrum indicates that at —15 °C the concentrations of nitrate and nitronium ion are 0-37 mol 1 and 0 34 mol 1 , respectively. The infra-red spectrum of nitric acid shows absorption bands characteristic of the nitronium ion. The equivalence of the concentrations of nitronium and nitrate ions argues against the importance of the following equilibrium ... 

The state of aqueous solutions of nitric acid In strongly acidic solutions water is a weaker base than its behaviour in dilute solutions would predict, for it is almost unprotonated in concentrated nitric acid, and only partially protonated in concentrated sulphuric acid. The addition of water to nitric acid affects the equilibrium leading to the formation of the nitronium and nitrate ions ( 2.2.1). The intensity of the peak in the Raman spectrum associated with the nitronium ion decreases with the progressive addition of water, and the peak is absent from the spectrum of solutions containing more than about 5% of water a similar effect has been observed in the infra-red spectrum. ... 

Solutions of dinitrogen pentoxide in nitric acid or sulphuric acid exhibit absorptions in the Raman spectrum at 1050 and 1400 cm with intensities proportional to the stoichiometric concentration of dinitrogen pentoxide, showing that in these media the ionization of dinitrogen pentoxide is complete. Concentrated solutions in water (mole fraction of NgOg > 0-5) show some ionization to nitrate and nitronium ion. Dinitrogen pentoxide is not ionized in solutions in carbon tetrachloride, chloroform or nitromethane. ... 

In aqueous solutions of sulphuric (< 50%) and perchloric acid (< 45 %) nitrous acid is present predominantly in the molecular form, although some dehydration to dinitrogen trioxide does occur.In solutions contairdng more than 60 % and 65 % of perchloric and sulphuric acid respectively, the stoichiometric concentration of nitrous acid is present entirely as the nitrosonium ion (see the discussion of dinitrogen trioxide 4.1). Evidence for the formation of this ion comes from the occurrence of an absorption band in the Raman spectrum almost identical with the relevant absorption observed in crystalline nitrosonium perchlorate. Under conditions in which molecular nitrous... 

The Raman spectrum can be used to give additional information regarding the symmetry properties of vibrations. This information derives from the measurement of the depolarization ratio p for each Raman band. The quantity p is a measure of the degree to which the polarization properties of the incident radiation may be changed after scattering... 

Nitrophenyl groups covalently bonded to classy carbon and graphite surfaces have been detected and characterized by unenhanced Raman spectroscopy in combination with voltammetry and XPS [4.292]. Difference spectra from glassy carbon with and without nitrophenyl modification contained several Raman bands from the nitrophenyl group with a comparatively large signal-to-noise ratio (Fig. 4.58). Electrochemical modification of the adsorbed monolayer was observed spectrally, because this led to clear changes in the Raman spectrum. 

The Raman spectrum in Fig. 10 for solid Ceo shows 10 strong Raman lines, the number of Raman-allowed modes expected for the intramolecular modes of the free molecule [6, 94, 92, 93, 95, 96, 97]. As first calculated by Stanton and Newton [98], the normal modes in molecular Ceo above about 1000 cm involve carbon atom displacements that are predominantly tangential... 

Similar results were found by Bacsa el al. [26] for cathode core material. Raman scattering spectra were reported by these authors for material shown in these figures, and these results are discussed below. Their HRTEM images showed that heating core material in air induces a clear reduction in the relative abundance of the carbon nanoparticles. The Raman spectrum of these nanoparticles would be expected to resemble an intermediate between a strongly disordered carbon black synthesized at 850°C (Fig. 2d) and that of carbon black graphitized in an inert atmosphere at 2820°C (Fig. 2c). As discussed above in section 2, the small particle size, as well as structural disorder in the small particles (dia. —200 A), activates the D-band Raman scattering near 1350 cm . ... 

The Raman spectrum of aqueous mer-cury(I) nitrate has, in addition to lines characteristic of the N03 ion, a strong absorption at 171.7 cm which is not found in the spectra of other metal nitrates and is not active in the infrared it is therefore diagnostic of the Hg-Hg stretching vibration since homonuclear diatomic vibrations are Raman active not infrared active. Similar data have subsequently been produced for a number of other compounds in the solid state and in solution. 

The short Os-Os bonds in Os2X correspond to triple bonds and give rise to stretching vibrations associated with bands around 280 cm-1 in the Raman spectrum (Table 1.6). 

It is an intensely reactive and hygoscopic yellow-brown substance (m.p. 75-78°C) its volatility suggests a low molecular mass Mossbauer spectra indicate 6-coordinate gold while the Raman spectrum is interpreted in terms of cw-bridged octahedral units. In the gas phase at 170°C, it comprises dimers and trimers [29] (electron diffraction). 

There have been some investigations into adsorption on zeolites (1, 2), and Greenler and Slager (3) have outlined a method for obtaining the Raman spectrum of a thin solid film deposited on a reflecting silver surface. 

The third common level is often invoked in simplified interpretations of the quantum mechanical theory. In this simplified interpretation, the Raman spectrum is seen as a photon absorption-photon emission process. A molecule in a lower level k absorbs a photon of incident radiation and undergoes a transition to the third common level r. The molecules in r return instantaneously to a lower level n emitting light of frequency differing from the laser frequency by —>< . This is the frequency for the Stokes process. The frequency for the anti-Stokes process would be + < . As the population of an upper level n is less than level k the intensity of the Stokes lines would be expected to be greater than the intensity of the anti-Stokes lines. This approach is inconsistent with the quantum mechanical treatment in which the third common level is introduced as a mathematical expedient and is not involved directly in the scattering process (9). 

For a vibration to be observable in the Raman spectrum there must be a change in molecular polarizability during the vibration. 

Hence we may conclude for a vibration to be active in the Raman spectrum it must have the same symmetry properties (i.e. transform in the same way),... 

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