Nonequilibrium free-energy relations for thermal changes
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Bernhardt, Debra
Evans, Denis J.
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George Basbas, Jack Sandweiss, Reinhardt B. Schuhmann, Stanley G. Brown
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Abstract
The Jarzynski equality and the Crooks fluctuation theorem enable the calculation of the change in a system's free energy from nonequilibrium path integrals. These relations consider processes where the system is driven out of equilibrium by a mechanical external agent while remaining in contact with a thermal reservoir at a fixed temperature. We generalize these relations to describe processes driven by any type of external agent, be it thermal or mechanical. Attention is given to the case of a system, initially in equilibrium, that is driven through a temperature change by a heat reservoir. The results are cast in a form applicable to experiments.
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Physical Review Letters
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100
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© 2008 American Physical Society. This is the author-manuscript version of this paper. Reproduced in accordance with the copyright policy of the publisher. Please refer to the journal link for access to the definitive, published version.
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Mathematical sciences
Physical sciences
Engineering