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2008-01-16

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/134218

Failure of the Work-Hamiltonian Connection for Free-Energy Calculations

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https://doi.org/10.1103/PhysRevLett.100.020601

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.

Subject

Mecànica estadística, Molècules

Subject (English)

Statistical mechanics, Molecules

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Articles publicats en revistes (Física de la Matèria Condensada)

Citation

VILAR, J. M. G. (José M. G.) and RUBÍ CAPACETI, José Miguel. Failure of the Work-Hamiltonian Connection for Free-Energy Calculations. Physical Review Letters. 2008. Vol. 100, num. 2, pags. 020601. ISSN 0031-9007. [consulted: 11 of August of 2026]. Available at: https://hdl.handle.net/2445/134218

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