Simulating fluid-solid equilibrium with the Gibbs ensemble

Sweatman, M.B. and Quirke, N. (2004) Simulating fluid-solid equilibrium with the Gibbs ensemble. Molecular Simulation, 30 (1). pp. 23-28. ISSN 1029-0435 (https://doi.org/10.1080/08927020310001626238)

[thumbnail of strathprints013476.pdf]
Preview
 PDF. Filename: strathprints013476.pdf
Accepted Author Manuscript
Download (131kB)| Preview

Abstract

The Gibbs ensemble is employed to simulate fluid-solid equilibrium for a shifted-force Lennard-Jones system. This is achieved by generating an accurate canonical Helmholtz free-energy model of the (defect-free) solid phase. This free-energy model is easily generated, with accuracy limited only by finite-size effects, by a single isothermal-isobaric simulation at a pressure not too far from coexistence for which the chemical potential is known. We choose to illustrate this method at the known triple-point because the chemical potential is easily calculated from the coexisting gas. Alternatively, our methods can be used to locate fluid-solid coexistence and the triple-point of pure systems if the chemical potential of the solid phase can be efficiently calculated at a pressure not too far from the actual coexistence pressure. Efficient calculation of the chemical potential of solids would also enable the Gibbs ensemble simulation of bulk solid-solid equilibrium and the grand-canonical ensemble simulation of bulk solids.

CORE (COnnecting REpositories)