The generalized Replica Exchange Method (gREM) is extended into the isobaric-isothermal ensemble, and applied to simulate a vapor-liquid phase transition in Lennard-Jones fluids. Merging an optimally designed generalized ensemble sampling with replica exchange, gREM is particularly well suited for the effective simulation of first-order phase transitions characterized by “backbending” in the statistical temperature. While the metastable and unstable states in the vicinity of the first-order phase transition are masked by the enthalpy gap in temperature replica exchange method simulations, they are transformed into stable states through the parameterized effective sampling weights in gREM simulations, and join vapor and liquid phases with a succession of unimodal enthalpy distributions. The enhanced sampling across metastable and unstable states is achieved without the need to identify a “good” order parameter for biased sampling. We performed gREM simulations at various pressures below and near the critical pressure to examine the change in behavior of the vapor-liquid phase transition at different pressures. We observed a crossover from the first-order phase transition at low pressure, characterized by the backbending in the statistical temperature and the “kink” in the Gibbs free energy, to a continuous second-order phase transition near the critical pressure. The controlling mechanisms of nucleation and continuous phase transition are evident and the coexistence properties and phase diagram are found in agreement with literature results.
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14 March 2013
Research Article|
March 14 2013
Order parameter free enhanced sampling of the vapor-liquid transition using the generalized replica exchange method
Qing Lu;
Qing Lu
1Division of Materials Science and Engineering,
Boston University
, Brookline, Massachusetts 02446, USA
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Jaegil Kim;
Jaegil Kim
a)
2Department of Chemistry,
Boston University
, Boston, Massachusetts 02215, USA
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John E. Straub
John E. Straub
b)
2Department of Chemistry,
Boston University
, Boston, Massachusetts 02215, USA
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a)
Present address: Broad Institute of MIT and Harvard, Cambridge, Massachusetts 02142, USA.
b)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 138, 104119 (2013)
Article history
Received:
January 08 2013
Accepted:
February 25 2013
Citation
Qing Lu, Jaegil Kim, John E. Straub; Order parameter free enhanced sampling of the vapor-liquid transition using the generalized replica exchange method. J. Chem. Phys. 14 March 2013; 138 (10): 104119. https://doi.org/10.1063/1.4794786
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