Theory of the effect of intermolecular interactions on the Raman spectra of liquid CHCl3and CFCl3

Abstract

A theory of weak intermolecular interactions is presented which indicates how association in the liquid state can manifest itself in vibration spectra. The theory is applied in this case to CHCl₃ and CFCl₃. The calculations predict which bands are most sensitive to the effects of intermolecular interaction. Previous experimental observations on the behaviour of the a ₁ vibrations of these molecules are reproduced. The calculations also predicted new features in the behaviour of the degenerate vibrations which were confirmed experimentally. The method lends itself to the study of solvent effects on vibration spectra in general.