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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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 9; pp. 3197 - 3215
Main Author: Käb, Günter
Format: Journal Article
Language:English
Published: United States American Chemical Society 09-03-2006
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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.
Bibliography:Part of the special issue “Jürgen Troe Festschrift”.
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ISSN:1089-5639
1520-5215
DOI:10.1021/jp054577k