Journal
THEORETICAL CHEMISTRY ACCOUNTS
Volume 128, Issue 2, Pages 147-155Publisher
SPRINGER
DOI: 10.1007/s00214-010-0834-3
Keywords
Vibrational relaxation; Liquids
Categories
Funding
- NSF [CHE-0750307]
- DOE [DE-FG02-09ER16110]
Ask authors/readers for more resources
A theoretical/computational framework for determining vibrational energy relaxation rates, pathways, and mechanisms, for small molecules and ions in liquids, is presented. The framework is based on the system-bath coupling approach, Fermi's golden rule, classical time-correlation functions, and quantum correction factors. We provide results for three specific problems: relaxation of the oxygen stretch in neat liquid oxygen at 77 K, relaxation of the water bend in chloroform at room temperature, and relaxation of the azide ion anti-symmetric stretch in water at room temperature. In each case, our calculated lifetimes are in reasonable agreement with experiment. In the latter two cases, theory for the observed solvent isotope effects illuminates the relaxation pathways and mechanisms. Our results suggest several propensity rules for both pathways and mechanisms.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available