Raman scattering from binary mixtures of van der Waals liquids. Theory of band profiles

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Abstract
A theory is proposed describing Raman band profiles of binary mixtures of van der Waals liquids. Extensive use is made of the fact that the Hamiltonian of these systems is invariant under permutations of molecules of the same chemical species. It is shown that the evolution of the half-width of a Raman band with concentration varies according to whether vibrational modulation is slow or fast. Widely different spectral effects are predicted for ‘‘chemical’’ and isotopic solutions. This difference is due to the fluctuations of the chemical composition in a given site of the liquid and to the structure-breaking effects which are present in the former case and absent in the latter.