Entropy production fluctuation theorem and the nonequilibrium work relation for free energy differences

Gavin E. Crooks
Phys. Rev. E 60, 2721 – Published 1 September 1999
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Abstract

There are only a very few known relations in statistical dynamics that are valid for systems driven arbitrarily far-from-equilibrium. One of these is the fluctuation theorem, which places conditions on the entropy production probability distribution of nonequilibrium systems. Another recently discovered far from equilibrium expression relates nonequilibrium measurements of the work done on a system to equilibrium free energy differences. In this paper, we derive a generalized version of the fluctuation theorem for stochastic, microscopically reversible dynamics. Invoking this generalized theorem provides a succinct proof of the nonequilibrium work relation.

  • Received 17 February 1999

DOI:

Authors & Affiliations

Gavin E. Crooks*

  • Department of Chemistry, University of California at Berkeley, Berkeley, California 94720

  • *Electronic address: gavinc@garnet.berkeley.edu

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Issue

Vol. 60, Iss. 3 — September 1999

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