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Title: Failure of the Work-Hamiltonian Connection for Free-Energy Calculations
Author: Vilar, J. M. G. (José M. G.), 1972-
Rubí Capaceti, José Miguel
Keywords: Mecànica estadística
Statistical mechanics
Issue Date: 16-Jan-2008
Publisher: American Physical Society
Abstract: Extensions of statistical mechanics are routinely being used to infer free energies from the work performed over single-molecule nonequilibrium trajectories. A key element of this approach is the ubiquitous expression d W / d t = ∂ H ( x , t ) / ∂ t , which connects the microscopic work W performed by a time-dependent force on the coordinate x with the corresponding Hamiltonian H ( x , t ) at time t . Here we show that this connection, as pivotal as it is, cannot be used to estimate free-energy changes. We discuss the implications of this result for single-molecule experiments and atomistic molecular simulations and point out possible avenues to overcome these limitations.
Note: Reproducció del document publicat a:
It is part of: Physical Review Letters, 2008, vol. 100, num. 2, p. 020601
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ISSN: 0031-9007
Appears in Collections:Articles publicats en revistes (Física de la Matèria Condensada)

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