Static dielectric properties of the Stockmayer fluid from computer simulation

Abstract

A number of summation methods for simulating polar liquids are compared using the Stockmayer potential fluid. The nearest image convention is found to have thermodynamic properties dependent on the cell shape. Spherical truncation and a summation proposed by Smith and Perram give reasonable agreement with the thermodynamic properties found from other methods but are not suitable for determining dielectric properties. The reaction field and Ewald-Kornfeld summation methods are in close agreement on the thermodynamic properties and have some measure of agreement on dielectric properties. However, the correlation function h Δ(r) clearly shows the effect of the truncation of the direct dipole-dipole interaction. It is concluded that an Ewald summation is the most appropriate method for simulating polar liquids. Thermodynamic and static dielectric properties of the Stockmayer fluid, determined from Monte Carlo and molecular dynamics calculations using the Ewald-Kornfeld summation, are presented. Calculations with large applied fields have been made to study dielectric saturation. The local field is examined in some detail and a distinction is made between Onsager's analysis of the local field into two components, which is supported by the present results, and Onsager's model for polar liquids which provides values for these components that do not agree well with the present results.