Vibrational energy relaxation of small molecules and ions in liquids |
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Authors: | J L Skinner |
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Institution: | (1) Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA |
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Abstract: | 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. |
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