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Quantum decoherence in mixed quantum-classical systems: Nonadiabatic processes

J. Chem. Phys. 103, 8130 (1995); doi:10.1063/1.470177

Issue Date: 8 November 1995

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Eric R. Bittner and Peter J. Rossky
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712
We address the issue of quantum decoherence in mixed quantum-classical simulations. We demonstrate that restricting the classical paths to a single path among all the quantum paths affects a coarse graining of the quantum paths. Such coarse graining causes the quantum paths to lose coherence as the various possible classical paths associated with each quantum state diverge. This defines a reduction mapping of the quantum density matrix, and we derive a quantum master equation suitable for mixed quantum-classical systems. The equation includes two terms: first, the ordinary quantum Liouvillian which is parametrized by a single classical path, and second, a quantum decoherence term that includes both a coherence time and length scale which are determined by the dynamics of the classical paths. Model calculations for electronic coherence loss in nonadiabatic mixed quantum-classical dynamics are presented as examples. For a model charge transfer chemical reaction with nonadiabatic transitions, application of the present formulation reveals that nonadiabaticity is diminished as the decoherence timescale becomes shorter and adiabatic dynamics are recovered in the limit of rapid decoherence. ©1995 American Institute of Physics.
History: Received 26 June 1995; accepted 8 August 1995
Permalink: http://link.aip.org/link/?JCPSA6/103/8130/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Mj
    Physical chemistry Chemical kinetics Nonequilibrium kinetics
  • 82.20.Wt
    Physical chemistry Chemical kinetics Computational modeling; simulation
  • YEAR: 1995

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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