Thermal and structural properties of ionic fluids.

Abstract

The electrostatic interaction in ionic fluids is well known to give rise to a characteristic phase behavior and structure. Sometimes its long range is proposed to single out the electrostatic potential over other interactions with shorter ranges. Here the importance of the range for the phase behavior and the structure of ionic fluids is investigated by means of grandcanonical Monte Carlo simulations of the lattice restricted primitive model (LRPM). The long-ranged electrostatic interaction is compared to various types of short-ranged potentials obtained by sharp and/or smooth cutoff schemes. Sharply cutoff electrostatic potentials are found to lead to a strong dependence of the phase behavior and the structure on the cutoff radius. However, when combined with a suitable additional smooth cutoff, the short-ranged LRPM is found to exhibit quantitatively the same phase behavior and structure as the conventional long-ranged LRPM. Moreover, the Stillinger-Lovett perfect screening property, which is well known to be generated by the long-ranged electrostatic potential, is also fulfilled by short-ranged LRPMs with smooth cutoffs. By showing that the characteristic phase behavior and structure of ionic fluids can also be found in systems with short-ranged potentials, one can conclude that the decisive property of the electrostatic potential in ionic fluids is not the long range but rather the valency dependence.