By P Carey
Biochemical functions of Raman and Resonance Raman Spectroscopes.
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Extra info for Biochemical Applications of Raman and Resonance Raman Spectroscopes
47) thatr - re is very n small, we must consider terms in the expansion containing (r - re) in which η is greater than 2. These higher-order terms introduce anharmonicity into the description of the nuclei motions. As a consequence, the simple selection rule stated in Section V that vibrational transitions are only allowed between levels differing in quantum numbers by ± 1 no longer applies universally. In addition to the fundamental transitions with Δι; = ± 1, overtones can occur in which Δυ > ± 1.
In contrast, the motion of 1 the nuclei in the v2 and vA modes of frequency 218 and 314 cm" (Fig. 75 for both these non-totally-symmetric vibrations. As is mentioned in Chapter 3, Section I,B,3, these vibrations provide a good test for checking that the Raman instrument is correctly set up for measuring depolarization ratios. Under resonance or near resonance conditions in certain rather rare a instances g Φ 0. 75. In the limiting case when g = g° = 0, but g Φ 0, the 3 0 phenomenon of inverse polarization occurs with, in theory, ρ = .
For strongly scattering samples, filters are used to provide a clean Raman spectrum uncluttered by laser-plasma lines—although the latter can provide excellent frequency standards for the calibration of Raman peak positions. For very accurate depolarization ratio measurements a polarizer is also placed before the focusing lens. The polarizer eliminates any light whose Ε vector differs in direction from that of the required orientation. For most depolarization measurements of biological molecules a polarizer is not essential.
Biochemical Applications of Raman and Resonance Raman Spectroscopes by P Carey