Nonequilibrium free-energy relations for thermal changes

Stephen R. Williams, Debra J. Searles, Denis J. Evans

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    35 Citations (Scopus)


    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.

    Original languageEnglish
    Article number250601
    JournalPhysical Review Letters
    Issue number25
    Publication statusPublished - 26 Jun 2008


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