Continuous distributions of charges: Extensions of the one component plasma

Abstract

The electrostatic interaction between finite charge distributions, ρ(r), in a neutralizing background is considered as an extension of the one component plasma (OCP) model of point charges. A general form for the interaction potential is obtained which can be applied to molecular theories of many simple charged fluids and mixtures and to the molecular dynamics (MD) simulation of such systems. The formalism is applied to the study of a fluid of Gaussian charges in a neutralizing background by MD simulation and using hypernetted-chain integral equation theory. The treatment of these interactions is extended to a periodic system using a Fourier Transform formulation and, for a rapidly decaying charge distribution, an application of the Ewald method. The contributions of the self-energy and neutralizing background to the system's energy are explicitly included in the formulation. Calculations reveal differences in behavior from the OCP model when the Wigner-Seitz radius is of order and less than the Gaussian charge density decay length. For certain parameter values these systems can exhibit a multiple occupancy crystalline phase at high density which undergoes re-entrant melting at higher density. An exploration of the effects of the various length scales of the system on the equation of state and radial distribution function is made.