Statistical Inhomogeneous Broadening of Infrared and Raman Transitions in Highly Vibrationally Excited XY₆ Molecules

Abstract

Simulations of the spectra of vibrational transitions in highly vibrationally excited XY 6 molecules at certain energy E vib are performed. The infrared (IR) transitions in the mode ν 3 of the molecules SF 6 and WF 6 as well as the Raman ones in the mode ν 1 of SF 6 are studied. The shapes and parameters of the spectral bands, such as the integral intensity, the mean frequency, and the width, are obtained in a wide range of E vib . The calculated widths prove to be much broader than the expected contributions to them because of intramolecular vibrational relaxation (IVR); this indicates the dominant role of statistical inhomogeneous broadening in the width formation for the investigated molecules.