Elastic Rayleigh scattering

Figure 9.6 Elastic and inelastic scattering of incident light by molecules. Rayleigh, elastic scattering Stokes and anti-Stokes, inelastic scattering. (Reproduced from P. Hendra, P.C. Jones, and G. Warnes, Fourier Transform Raman Spectroscopy Instrumentation and Chemical Applications, Ellis Horwood, Chichester, 1991.)...

Spectroscopic examination of light scattered from a monochromatic probe beam reveals the expected Rayleigh, Mie, and/or Tyndall elastic scattering at unchanged frequency, and other weak frequencies arising from the Raman effect. Both types of scattering have appHcations to analysis. 

Figure 3. Energy schemata of transitions involving vibrational states (a excitation of 1st vibrational state - mid-IR absorption b excitation of overtone vibrations - near-IR absorptions c elastic scattering - Rayleigh lines d Raman scattering - Stokes lines e Raman scattering - Anti-Stokes lines f fluorescence).

In the case of solutions, concentration fluctuations only contribute to the central elastic part of the scattering spectrum. However, the Brownian movement of solute molecules creates weak frequency displacements that broaden the central peak. This phenomenon is called Rayleigh line broadening or quasielastic scattering [26-28]. This section deals with elastic scattering only. 

The interpretation given above is simplified, since fluorescence is not the only process that allows the atom to lose its excess energy. Other phenomena such as Rayleigh scattering (elastic scattering) and the Compton effect (inelastic scattering with release of Compton electrons) can complicate the X-ray emission spectrum. 

Development of laser sources was followed by the use of special monochromators that can resolve the more-intense, elastically scattered light (Rayleigh line) from the weak, inelastically scattered, Raman signal. The requirement of frequency matching in the double or triple monochromators presents a challenging, coupling problem for frequency-scanning systems. 

These results apply specifically to Rayleigh, or elastic, scattering. For Raman, or inelastic, scattering the same basic CID expressions apply but with the molecular property tensors replaced by corresponding vibrational Raman transition tensors between the initial and final vibrational states nv and rn . In this way a s are replaced by (mv aap(Q) nv), where aQ/3(<3) s are effective polarizability and optical activity operators that depend parametrically on the normal vibrational coordinates Q such that, within the Placzek polarizability theory of the Raman effect [23], ROA intensity depends on products such as (daaf3 / dQ)0 dG af3 / dQ) and (daaf3 / dQ)0 eajS dAlSf / dQ)0. 

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