Communication: phase transitions, criticality, and three-phase coexistence in constrained cell models.
In simulation studies of fluid-solid transitions, the solid phase is usually modeled as a constrained system in which each particle is confined to move in a single Wigner-Seitz cell. The constrained cell model has been used in the determination of fluid-solid coexistence via thermodynamic integration and other techniques. In the present work, the phase diagram of such a constrained system of Lennard-Jones particles is determined from constant-pressure simulations. The pressure-density isotherms exhibit inflection points which are interpreted as the mechanical stability limit of the solid phase. The phase diagram of the constrained system contains a critical and a triple point. The temperature and pressure at the critical and the triple point are both higher than those of the unconstrained system due to the reduction in the entropy caused by the single occupancy constraint.
Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, California 90095, USA.
Michael
M
Nayhouse
Joseph Sang-Il
JS
Kwon
G
G
Orkoulas
D003198:Computer Simulation; D008956:Models, Chemical; D009010:Monte Carlo Method; D044367:Phase Transition; D013816:Thermodynamics