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Calculation of semiclassical free energy differences along nonequilibrium classical trajectories

J. Chem. Phys. 131, 164510 (2009); doi:10.1063/1.3253799

Published 29 October 2009

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M. F. Gelin1 and D. S. Kosov2
1Department of Chemistry, Technische Universität of München, Lichtenbergstrasse 4, D-85747 Garching, Germany
2Department of Physics and Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles, Campus Plaine, CP 231, Blvd. du Triomphe, B-1050 Brussels, Belgium and Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA
We have derived several relations, which allow the evaluation of the system free energy changes in the leading order in [h-bar]2 along classically generated trajectories. The results are formulated in terms of purely classical Hamiltonians and trajectories, so that semiclassical partition functions can be computed, e.g., via classical molecular dynamics simulations. The Hamiltonians, however, contain additional potential-energy terms, which are proportional to [h-bar]2 and are temperature-dependent. We discuss the influence of quantum interference on the nonequilibrium work and problems with unambiguous definition of the semiclassical work operator. ©2009 American Institute of Physics
History: Received 30 April 2009; accepted 5 October 2009; published 29 October 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/164510/1
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KEYWORDS and PACS

Keywords
PACS
  • 65.20.Jk
    Studies of thermodynamic properties of specific liquids
  • 61.20.Ja
    Computer simulation of liquid structure
  • YEAR: 2009

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PUBLICATION DATA

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