Vibrational dephasing of the C-Br stretching modes in gauche and trans dibromoethane

Abstract

The isotropic Raman spectra of the gauche and trans C-Br stretching modes in 1,2-dibromoethane were studied as a function of temperature in the liquid phase. Isotropic dephasing times were found to be longer for the gauche conformer, and decreased at higher temperatures for both rotamers. Vibrational second moments were observed to be greater for the trans species. Application of the isolated binary collision model to this system could not reproduce the experimentally observed temperature dependence of τ_iso. Values of the modulation times obtained from the Kubo lineshape formalism are in qualitative agreement with Enskog hard-sphere collision times. This approach was also used to provide a qualitative explanation of the longer observed modulation times in the gauche conformer.