Calculation of semiclassical free energy differences along nonequilibrium classical trajectories.
We have derived several relations, which allow the evaluation of the system free energy changes in the leading order in variant Planck's over 2pi(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 variant Planck's over 2pi(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.
Gelin
M F
MF
Department of Chemistry, Technische Universität of München, Lichtenbergstrasse 4, D-85747 Garching, Germany. gelin@ch.tum.de
Kosov
D S
DS