Microscopic analysis of Clausius-Duhem processes

Abstract

Given a thermodynamic process which carries a system from one equilibrium state to another, we construct a quantity whose average, over an ensemble of microscopic realizations of the process, depends only on these end states, even if at intermediate times the system is out of equilibrium. This result: (1) can be used to express the entropy difference between two equilibrium states in terms of an irreversible process connecting them, (2) leads to two statistical statements of the Clausius-Duhem inequality, and (3) can be generalized to situations in which the system begins and/or ends in nonequilibrium states.

12 pages + 1 figure; some new material added, but basic result unchanged

References in corpus (3)

• A nonequilibrium equality for free energy differences
• The Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences
• Annealed Importance Sampling

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