Equilibrium free-energy differences from nonequilibrium measurements: A master-equation approach

Abstract

In has recently been shown that the Helmholtz free-energy difference between two equilibrium configurations of a system may be obtained from an ensemble of finite-time (nonequilibrium) measurements of the work performed in switching an external parameter of the system. Here this result is established, as an identity, within the master equation formalism. Examples are discussed and numerical illustrations provided. © 1997 The American Physical Society.