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Pure Appl. Chem., 2007, Vol. 79, No. 8, pp. 1361-1368

Verification of time-reversibility requirementfor systems satisfying the Evans-Searles fluctuation theorem

Emil Mittag, Denis J. Evans and Stephen R. Williams

Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia

Abstract: The Evans-Searles fluctuation theorem (ESFT) has been shown to be applicable in the near- and far-from-equilibrium regimes for systems with both constant and time-dependent external fields. The derivations of the ESFT have assumed that the external field has a definite parity under a time-reversal mapping. In the present paper, we confirm that the time-reversibility of the system dynamics is a necessary condition for the ESFT to hold. The manner in which the ESFT fails for systems that are not time-reversible is presented, and results are shown which demonstrate that systems which fail to satisfy the ESFT may still satisfy the Crooks relation (CR).