Article

Simulation of phase boundaries using constrained cell models.

Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA 90095, USA.
Journal of Physics Condensed Matter (Impact Factor: 2.22). 08/2012; 24(37):375105. DOI: 10.1088/0953-8984/24/37/375105
Source: PubMed

ABSTRACT Despite impressive advances, precise simulation of fluid-fluid and fluid-solid phase transitions still remains a challenging task. The present work focuses on the determination of the phase diagram of a system of particles that interact through a pair potential, φ(r), which is of the form φ(r) = 4ε[(σ/r)(2n) - (σ/r)(n)] with n = 12. The vapor-liquid phase diagram of this model is established from constant-pressure simulations and flat-histogram techniques. The properties of the solid phase are obtained from constant-pressure simulations using constrained cell models. In the constrained cell model, the simulation volume is divided into Wigner-Seitz cells and each particle is confined to moving in a single cell. The constrained cell model is a limiting case of a more general cell model which is constructed by adding a homogeneous external field that controls the relative stability of the fluid and the solid phase. Fluid-solid coexistence at a reduced temperature of 2 is established from constant-pressure simulations of the generalized cell model. The previous fluid-solid coexistence point is used as a reference point in the determination of the fluid-solid phase boundary through a thermodynamic integration type of technique based on histogram reweighting. Since the attractive interaction is of short range, the vapor-liquid transition is metastable against crystallization. In the present work, the phase diagram of the corresponding constrained cell model is also determined. The latter is found to contain a stable vapor-liquid critical point and a triple point.

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