title: Entropy-energy decomposition from nonequilibrium work trajectories.
abstract: We derive expressions for the equilibrium entropy and energy changes in the context of the Jarzynski equality relating nonequilibrium work to equilibrium free energy. The derivation is based on a stochastic path integral technique that reweights paths at different temperatures. Stochastic dynamics generated by either a Langevin equation or a Metropolis Monte Carlo scheme are treated. The approach enables the entropy-energy decomposition from trajectories evolving at a single-temperature and does not require simulations or measurements at two or more temperatures. Both finite difference and analytical formulae are derived. Testing is performed on a prototypical model system and the method is compared with existing thermodynamic integration and thermodynamic perturbation approaches for entropy-energy decomposition. The new formulae are also put in the context of more general, dynamics-independent expressions that derive from either a fluctuation theorem or the Feynman-Kac theorem.
authors.affiliation: Department of Chemistry and The Center for Computational Medicine and Biology, University of Michigan, Ann Arbor, Michigan 48109, USA.
authors.forename: Jeremiah
authors.initials: J
authors.lastname: Nummela
authors.forename: Faten
authors.initials: F
authors.lastname: Yassin
authors.forename: Ioan
authors.initials: I
authors.lastname: Andricioaei
mesh_terms: D003198:Computer Simulation; D019277:Entropy; D008956:Models, Chemical; D013816:Thermodynamics