The effect of solvent configuration on matrix-isolation solute line shapes

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Abstract
A theory of the vibrational spectral line shape for matrix-isolated species is presented which is based on the perturbing influence of the solvent packing on a given normal mode of the solute. The theory is shown to be remarkably accurate in predicting relative line shapes in detail and in predicting absolute shifts of lines from site to site. Application of the theory to experimental spectra of OCS in Ar and Xe matrices has allowed assignment of the major features of the spectra to solvent sites of two general classes: one that is cage or crystalline in nature and the other that is cluster or amorphous in nature.