Complex vibrational correlation functions extracted from the resolved ν2 band of liquid acetonitrile

Abstract

The development of a sophisticated model is presented for fitting the experimental Raman spectra of liquid acetonitrile. A new approach for extracting all possible band shape details of highly overlapping spectral bands is derived and implemented. A unique, statistically justified resolution is obtained of the ν₂ vibrational band into its components at 25, 50 and 75°C. The parameters of both the real and imaginary parts of the vibrational correlation functions are reported for the first time together with their confidence intervals. The quantitative characteristics obtained of the ν₂ mode dynamics can be considered as experimental data and used for testing theoretical models of vibrational relaxation.