Measurement of nonequilibrium entropy from space-time thermodynamic integration

• Published in: The Journal of chemical physics Vol. 129; no. 2; p. 024116
• Main Authors: Athènes, Manuel, Adjanor, Gilles
• Format: Journal Article
• Language: English
• Published: United States 14.07.2008
• ISSN: 1089-7690
• DOI: 10.1063/1.2953328

The entropy of a system transiently driven out of equilibrium by a time-inhomogeneous stochastic dynamics is first expressed as a transient response function generalizing the nonlinear Kawasaki-Crooks response. This function is then reformulated into three statistical averages defined over ensembles of nonequilibrium trajectories. The first average corresponds to a space-time thermodynamic perturbation relation, while the two following ones correspond to space-time thermodynamic integration relations. Provided that trajectories are initiated starting from a distribution of states that is analytically known, the ensemble averages are computationally amenable to Markov chain Monte Carlo methods. The relevance of importance sampling in path ensembles is confirmed in practice by computing the nonequilibrium entropy of a driven toy system. We finally study a situation where the dynamics produces entropy. In this case, we observe that space-time thermodynamic integration still yields converged estimates, while space-time thermodynamic perturbation turns out to converge very slowly.