Entropy-energy decomposition from nonequilibrium work trajectories |
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Authors: | Nummela Jeremiah Yassin Faten Andricioaei Ioan |
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Institution: | Department of Chemistry and The Center for Computational Medicine and Biology, University of Michigan, Ann Arbor, Michigan 48109, USA. |
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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. |
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