An approach for directly determining the liquid–vapor phase equilibrium of a model system at any temperature along the coexistence line is described. The method relies on transition matrix Monte Carlo ideas developed by Fitzgerald, Picard, and Silver [Europhys. Lett. 46, 282 (1999)]. During a Monte Carlo simulation attempted transitions between states along the Markov chain are monitored as opposed to tracking the number of times the chain visits a given state as is done in conventional simulations. Data collection is highly efficient and very precise results are obtained. The method is implemented in both the grand canonical and isothermal–isobaric ensemble. The main result from a simulation conducted at a given temperature is a density probability distribution for a range of densities that includes both liquid and vapor states. Vapor pressures and coexisting densities are calculated in a straightforward manner from the probability distribution. The approach is demonstrated with the Lennard-Jones fluid. Coexistence properties are directly calculated at temperatures spanning from the triple point to the critical point.
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8 June 2003
Research Article|
June 08 2003
Direct calculation of liquid–vapor phase equilibria from transition matrix Monte Carlo simulation
Jeffrey R. Errington
Jeffrey R. Errington
Department of Chemical Engineering, University at Buffalo, The State University of New York, Buffalo, New York 14260
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J. Chem. Phys. 118, 9915–9925 (2003)
Article history
Received:
January 15 2003
Accepted:
March 13 2003
Citation
Jeffrey R. Errington; Direct calculation of liquid–vapor phase equilibria from transition matrix Monte Carlo simulation. J. Chem. Phys. 8 June 2003; 118 (22): 9915–9925. https://doi.org/10.1063/1.1572463
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