Entropy-energy decomposition from nonequilibrium work trajectories.
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.
Nummela
Jeremiah
J
Department of Chemistry and The Center for Computational Medicine and Biology, University of Michigan, Ann Arbor, Michigan 48109, USA.
Yassin
Faten
F
Andricioaei
Ioan
I
D003198:Computer Simulation; D019277:Entropy; D008956:Models, Chemical; D013816:Thermodynamics