The restricted primitive model of ionic fluids with nonadditive diameters

Abstract

The restricted primitive model with nonadditive hard-sphere diameters is shown to have interesting and peculiar clustering properties. We report accurate calculations of the cluster concentrations. Implementing efficient and ad hoc Monte Carlo algorithms we determine the effect of nonadditivity on both the clustering and the gas-liquid binodal. For negative nonadditivity, tending to the extreme case of completely overlapping unlike ions, the prevailing clusters are made of an even number of particles having zero total charge. For positive nonadditivity, the frustrated tendency to segregation of like particles and the reduced space available to the ions favors percolating clusters at high densities.