Raman line shape study of the ν1 band of chloroform in a polar solvent

Abstract

The polarized and depolarized spectra of CHCl3 in CD3CN (and CDCl3 in CH3CN) were utilized to obtain reorientational and vibrational relaxation correlation functions for the carbon–hydrogen stretching mode. The effect of the polar solvent on molecular reorientation is discussed and compared with earlier studies performed in nonpolar solvents. The recently proposed model of vibrational dephasing has been applied to analyze the isotropic correlation functions obtained for these systems, and an explanation has been proposed to interpret the anomalously greater efficiency of vibrational relaxation for the ν1 mode in CHCl3, compared to that observed in CDCl3.