Infrared and Raman study of liquids. III. Theory of the rotation-vibration coupling effects. Diatomic molecules in inert solutions

Abstract

A theory is proposed to explain the effects of the rotation-vibration coupling in the ir and Raman spectra of inert solutions of diatomic molecules. This theory is a stochastic-type theory related to similar theories of NMR spectra. Spectral manifestations of the rotation-vibration interaction are found to depend very strongly on whether an ir, isotropic, or anisotropic Raman spectrum is concerned, on the nature of molecular rotations in the liquid, and on the properties of the solvent-solute interaction forces. Explicit expressions are given for a number of profiles which are perturbed by this interaction.