Fewest Switches Adiabatic Surface Hopping As Applied to Vibrational Energy Relaxation
In this contribution quantum/classical surface hopping methodology is applied to vibrational energy relaxation of a quantum oscillator in a classical heat bath. The model of a linearly damped (harmonic) oscillator is chosen which can be mapped onto the Brownian motion (Caldeira−Leggett) Hamiltonian....
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Published in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 9; pp. 3197 - 3215 |
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Main Author: | |
Format: | Journal Article |
Language: | English |
Published: |
United States
American Chemical Society
09-03-2006
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Subjects: | |
Online Access: | Get full text |
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Summary: | In this contribution quantum/classical surface hopping methodology is applied to vibrational energy relaxation of a quantum oscillator in a classical heat bath. The model of a linearly damped (harmonic) oscillator is chosen which can be mapped onto the Brownian motion (Caldeira−Leggett) Hamiltonian. In the simulations Tully's fewest switches surface hopping scheme is adopted with inclusion of dephasing in the adiabatic basis using a simple decoherence algorithm. The results are compared to the predictions of a Redfield-type quantum master equation modeling using the classical heat bath force correlation function as input. Thereby a link is established between both types of quantum/classical approaches. Viewed from the latter perspective, surface hopping with dephasing may be interpreted as “on-the-fly” stochastic realization of a quantum/classical Pauli master equation. |
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Bibliography: | Part of the special issue “Jürgen Troe Festschrift”. istex:B631879D1BC23EC0D5752C1CDE5911FA70972BBF ark:/67375/TPS-CJMHZM7J-3 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp054577k |