Calculation of semiclassical free energy differences along nonequilibrium classical trajectories

Gelin, M.F.;Kosov, D.S.

Abstract

We have derived several relations, which allow the evaluation of the system free energy changes in the leading order in ℏ2 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 ℏ2 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.

Journal

Journal of Chemical Physics

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131

ISBN/ISSN

1089-7690

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Publisher

American Institute of Physics

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DOI

10.1063/1.3253799