A new approach for the calculation of vibrational energy relaxation rate constants is introduced. The new approach is based on linear response theory, and is shown to have several distinct advantages over the standard Landau–Teller formula, which is based on the Bloch–Redfield theory, namely: (1) weak system–bath coupling is not assumed; (2) selectivity in choosing the vibrational energy relaxation pathway, including non-Landau–Teller pathways, is possible; (3) the validity of rate kinetics can be explicitly verified; (4) direct extraction of the high-frequency tail of the force–force correlation function is avoided. A detailed analysis of the conditions under which the new expression reduces into the Landau–Teller formula, and an application in the case of bilinear coupling to a harmonic bath are provided.
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22 April 2003
Research Article|
April 22 2003
Vibrational energy relaxation rate constants from linear response theory
Qiang Shi;
Qiang Shi
Department of Chemistry and The FOCUS Center, University of Michigan, Ann Arbor, Michigan 48109-1055
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Eitan Geva
Eitan Geva
Department of Chemistry and The FOCUS Center, University of Michigan, Ann Arbor, Michigan 48109-1055
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J. Chem. Phys. 118, 7562–7571 (2003)
Article history
Received:
October 22 2002
Accepted:
January 29 2003
Citation
Qiang Shi, Eitan Geva; Vibrational energy relaxation rate constants from linear response theory. J. Chem. Phys. 22 April 2003; 118 (16): 7562–7571. https://doi.org/10.1063/1.1562611
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