Gibbs free-energy estimates from direct path-sampling computations.
We have implemented a path-sampling scheme enabling a direct estimation of Gibbs free energy. This scheme consists of a Monte Carlo sampling of constant-pressure Langevin paths, followed by an ensemble averaging carried out over the Markov chain of paths. In practice, we sample an umbrella path ensemble, which requires to rigorously define a statistical weight for the paths, equivalent of the Boltzmann weight. This statistical weight is a function of an effective work related to the path. The umbrella ensemble is chosen so that its work histogram overlaps with the histograms corresponding to the ensembles of forward and backward paths. We have finally investigated the relations between numerical efficiency and overlapping properties of the various work histograms. This analysis yields a built-in criterion for diagnosing the convergence during a single-run simulation.
Adjanor
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Service de Recherches de Métallurgie Physique, Commissariat à l'énergie Atomique-Saclay, 91191 Gif-sur-Yvette, France. gilles.adjanor@cea.fr
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