Computer simulations of the restricted primitive model at very low temperature and density

Abstract

The problem of successfully simulating ionic fluids at low temperature and low density states is well known in the simulation literature: using conventional methods, the system is not able to equilibrate rapidly due to the presence of strongly associated cation–anion pairs. In this paper we present a numerical method for speeding up computer simulations of the restricted primitive model (RPM) at low temperatures (around the critical temperature) and at very low densities (down to 10−10σ −3, where σ is the ion diameter). Experimentally, this regime corresponds to typical concentrations of electrolytes in nonaqueous solvents. As far as we are aware, this is the first time that the RPM has been equilibrated at such extremely low concentrations. More generally, this method could be used to equilibrate other systems that form aggregates at low concentrations