Studying vapor-liquid transition using a generalized ensemble

Date
2019-10-02
Authors
Ballal, Deepti
Lu, Qing
Raju, Muralikrishna
Song, Xueyu
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Altmetrics
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Song, Xueyu
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Ames Laboratory
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Chemistry
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Abstract

Homogeneous vapor-liquid nucleation is studied using the generalized Replica Exchange Method (gREM). The generalized ensemble allows the study of unstable states that cannot directly be studied in the canonical ensemble. Along with replica exchange, this allows for efficient sampling of the multiple states in a single simulation. Statistical Temperature Weighted Histogram Analysis Method is used for postprocessing to get a continuous free energy curve from bulk vapor to bulk liquid. gREM allows the study of planar, cylindrical, and spherical interfaces in a single simulation. The excess Gibbs free energy for the formation of a spherical liquid droplet in vapor for a Lennard-Jones system is calculated from the free energy curve and compared against the umbrella sampling results. The nucleation free energy barrier obtained from gREM is then used to calculate the nucleation rate without relying on any classification scheme for separating the vapor and liquid.

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Gas liquid interfaces, Thermodynamic functions, Statistical analysis, Replica exchange method, Equilibrium thermodynamics, Statistical thermodynamics, Free energy landscapes, Phase transitions, Monte Carlo methods
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