Free energy and phase equilibria for the restricted primitive model of ionic fluids from Monte Carlo simulations

Journal Article · Fri Jul 15 04:00:00 EDT 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.467770· OSTI ID:7103554

Orkoulas, G; Panagiotopoulos, A Z ^[1]

---

1. School of Chemical Engineering, Cornell University, Ithaca, New York 14853 (United States)

In this work, we investigate the liquid--vapor phase transition of the restricted primitive model of ionic fluids. We show that at the low temperatures where the phase transition occurs, the system cannot be studied by conventional molecular simulation methods because convergence to equilibrium is slow. To accelerate convergence, we propose cluster Monte Carlo moves capable of moving more than one particle at a time. We then address the issue of charged particle transfers in grand canonical and Gibbs ensemble Monte Carlo simulations, for which we propose a biased particle insertion/destruction scheme capable of sampling short interparticle distances. We compute the chemical potential for the restricted primitive model as a function of temperature and density from grand canonical Monte Carlo simulations and the phase envelope from Gibbs Monte Carlo simulations. Our calculated phase coexistence curve is in agreement with recent results of Caillol obtained on the four-dimensional hypersphere and our own earlier Gibbs ensemble simulations with single-ion transfers, with the exception of the critical temperature, which is lower in the current calculations. Our best estimates for the critical parameters are [ital T][sup *][sub [ital c]]=0.053, [rho][sup *][sub [ital c]]=0.025. We conclude with possible future applications of the biased techniques developed here for phase equilibrium calculations for ionic fluids.

• OSTI ID: 7103554
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 101:2; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

665000* -- Physics of Condensed Matter-- (1992-)
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
CALCULATION METHODS
ELECTROLYTES
ENERGY
EVAPORATION
FLUIDS
FREE ENERGY
GASES
LIQUIDS
MONTE CARLO METHOD
PHASE STUDIES
PHASE TRANSFORMATIONS
PHYSICAL PROPERTIES
SIMULATION
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
VAPORS