| Autor: |
Nummela, Jeremiah, Yassin, Faten, Andricioaei, Ioan |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 1/14/2008, Vol. 128 Issue 2, p024104, 7p, 3 Charts, 3 Graphs |
| Abstrakt: |
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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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