Scattering in Raman

FTIR spectroscopy is a class of vibrational spectroscopy similar to Raman spectroscopy which provides molecular-level information based on the absorption of electromagnetic radiation, rather than inelastic scattering in Raman. 

FIGURE 6-18 Inelastic scattering in Raman spectroscopy, (a) As incident radiaiion of frequency r impinges on the sample, molecules of the sample are excited from one of their ground vibrational slates to a higher so-called virtuaf state, indicated by the dashed level in (b). When the molecule relaxes, il may return to the first vibrational state as indicated and emit a photon of energy - /ifi-, r,) where i Is the frequency of the vibrational transition. Alter-... 

Although the three spectroscopic techniques are very different in several aspects, their basic physical origin is the same absorption in mid-IR and NIR, and scattering in Raman, as a consequence of molecular vibrations. Due to the different excitation conditions, the relationships between the observed spectral intensities and the chemical nature of the vibrating molecules vary significantly. 

We will now look at two-photon processes. We will concentrate on Raman scattering although two-photon absorption can be handled using the same approach. In Raman scattering, absorption of an incident photon of frequency coj carries... 

Vibrational spectroscopy provides detailed infonnation on both structure and dynamics of molecular species. Infrared (IR) and Raman spectroscopy are the most connnonly used methods, and will be covered in detail in this chapter. There exist other methods to obtain vibrational spectra, but those are somewhat more specialized and used less often. They are discussed in other chapters, and include inelastic neutron scattering (INS), helium atom scattering, electron energy loss spectroscopy (EELS), photoelectron spectroscopy, among others. 

Raman scattering and (b) anti-Stokes Raman scattering. In Stokes scattering, tlie cluomophore is initially in the ground vibrational state, g, and oi > CO2. hr spontaneous anti-Stokes scattering, the cluomophore must be initially m an excited vibrational state,/ Also note that in (b), M2 is (arbitrarily) defined as being greater than... 

With the advent of short pulsed lasers, investigators were able to perfonn time resolved coherent Raman scattering. In contrast to using femtosecond pulses whose spectral widtii provides the two colours needed to produce Raman coherences, discussed above, here we consider pulses having two distinct centre frequencies whose difference drives the coherence. Since the 1970s, picosecond lasers have been employed for this purpose [113. 114], and since the late 1980s femtosecond pulses have also been used [115]. Flere we shall briefly focus on the two-colour femtosecond pulsed experiments since they and the picosecond experiments are very similar in concept. 

The second excitation mechanism, impact scattering, involves a short range interaction between the electron and the molecule (put simply, a collision) which scatters the electrons over a wide range of angles. The usefiil feature of impact scattering is that all vibrations may be excited and not only the dipole active ones. As in Raman spectroscopy, the electron may also take an amount of energy hv away from excited molecules and leave the surface with an energy equal to Eq + hv. 

Electronic, vibrational and rotational transitions may be involved in Raman scattering but, in this chapter, we consider only rotational transitions. 

A number of reviews have appeared covering the various aspects of borate glasses. The stmcture, physical properties, thermochemistry, reactions, phase equihbria, and electrical properties of alkah borate melts and glasses have been presented (73). The apphcation of x-ray diffraction, nmr, Raman scattering, in spectroscopy, and esr to stmctural analysis is available (26). Phase-equihbrium diagrams for a large number of anhydrous borate systems are included in a compilation (145), and thermochemical data on the anhydrous alkah metal borates have been compiled (17). 

A dispersive element for spectral analysis of PL. This may be as simple as a filter, but it is usually a scanning grating monochromator. For excitation spectroscopy or in the presence of much scattered light, a double or triple monochromator (as used in Raman scattering) may be required. 

In Raman spectroscopy the intensity of scattered radiation depends not only on the polarizability and concentration of the analyte molecules, but also on the optical properties of the sample and the adjustment of the instrument. Absolute Raman intensities are not, therefore, inherently a very accurate measure of concentration. These intensities are, of course, useful for quantification under well-defined experimental conditions and for well characterized samples otherwise relative intensities should be used instead. Raman bands of the major component, the solvent, or another component of known concentration can be used as internal standards. For isotropic phases, intensity ratios of Raman bands of the analyte and the reference compound depend linearly on the concentration ratio over a wide concentration range and are, therefore, very well-suited for quantification. Changes of temperature and the refractive index of the sample can, however, influence Raman intensities, and the band positions can be shifted by different solvation at higher concentrations or... 

Raman scattering is essentially undelayed with respect to the arrival of the incident light, in this technique the detector is activated only during each laser pulse and deactivated at all other times. This allows only Raman signals to be recorded but fluorescence signals and detector noise are gated out (Fig. 19). Improvement in Raman signal to fluorescence ratio has been achieved as illustrated in Fig. 20. The technique, however, at present seems to be restricted by several instrumental limitations [37). 

De Santis A., Sampoli M., Morales P, Signorelli G. Density evolution of Rayleigh and Raman depolarized scattering in fluid N2. Mol. Phys. 35, 1125-40 (1978). 

Pemberton, J. E., Surface enhanced Raman scattering, in Electrochemical Interfaces, H. D. Abmna, Ed., VCH, Weinheim, Germany, 1991, p. 193. 

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