Monte Carlo simulation of the nonadditive restricted primitive model of ionic fluids: Phase diagram and clustering

Abstract

We report an accurate Monte Carlo calculation of the phase diagram and clustering properties of the restricted primitive model with nonadditive hard-sphere diameters. At high density the positively nonadditive fluid shows more clustering than in the additive model and the negatively nonadditive fluid shows less clustering than in the additive model; at low density the reverse scenario appears. A negative nonadditivity tends to favor the formation of neutrally charged clusters starting from the dipole. A positive nonadditivity favors the pairing of like ions at high density. The critical point of the gas-liquid phase transition moves at higher temperatures and higher densities for a negative nonadditivity and at lower temperatures and lower densities for a positive nonadditivity. The law of corresponding states does not seem to hold strictly. Our results can be used to interpret recent experimental works on room temperature ionic liquids.