Vibrational bandshapes of monohydric saturated alcohols

Abstract

Calculations are presented for three models of alcohols dissolved in carbon tetrachloride in the slow modulation limit. A number of liquidstate models is considered. The calculated bands differ markedly in some cases from the often assumed gaussian distribution. The Raman spectra of the OH-stretching vibration of methanol, t-butanol and adamantanol-1 in dilute CC1, solution are presented. It is concluded that the second moments of these bands compare well with the calculated values in two of the solvent models. The experimental bands are narrower than the computed bands, indicating some motional narrowing. Trends in the vapour-solution frequency shift are also well reproduced in the calculations.