Some Recent Advances in Free Energy and Sampling Methods for Crystals, Mixtures and Coexisting Phases

David Kofke
SUNY Buffalo

Many applications require knowledge of the free energy, but its calculation by work-based methods is notoriously prone to inaccuracy. We discuss a conceptual basis for understanding this behavior, and ways to detect and remedy it. We then describe applications to crystal phases, where sampling and free-energy calculations can be improved by exploiting the approximate harmonic character of the crystal. We then examine developments in the field obtained through the use of the Transition-Matrix Monte Carlo methods, presented in the context of mixtures, and finally we examine how some of the foregoing ideas can be applied to evaluate thermodynamic phase coexistence.

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