Vibrational energy relaxation of the OH(D) stretch fundamental of methanol in carbon tetrachloride

Tolga S Gulmen 3rd; Edwin L Sibert

doi:10.1063/1.2131055

Vibrational energy relaxation of the OH(D) stretch fundamental of methanol in carbon tetrachloride

J Chem Phys. 2005 Nov 22;123(20):204508. doi: 10.1063/1.2131055.

Authors

Tolga S Gulmen 3rd¹, Edwin L Sibert

Affiliation

¹ Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, WI 53706, USA.

PMID: 16351282
DOI: 10.1063/1.2131055

Abstract

The lifetimes of the hydroxyl stretch fundamentals of two methanol isotopomers, MeOH and MeOD, in carbon tetrachloride solvent are calculated through the use of the perturbative Landau-Teller and fluctuating Landau-Teller methods. Examination of these systems allows for insight into the nature of the vibrational couplings that lead to intramolecular vibrational energy transfer. While both systems display energy transfer to nearly degenerate modes, MeOD also displays strong coupling to an off-resonant vibration. The relaxation of MeOH and MeOD occurs through transitions involving a total change in the vibrational quanta of 4 and 3, respectively. We calculate vibrational energy relaxation lifetimes of 4-5 ps for MeOH and 2-3 ps for MeOD that agree well with the experimentally determined values.