Thermodynamic properties of polarizable Stockmayer fluids: perturbation theory and simulation

Abstract

Molecular dynamics simulations and perturbation theory calculations have been carried out for polarizable and non-polarizable Stockmayer fluids. pVT data are given for a polarizable Stockmayer fluid of varying dipolar strength covering the whole fluid region. For non-polarizable dipolar interaction potential models two sets of perturbation scheme calculations are compared with MD simulation results, to test the reliability of a perturbation theory over a range of temperature and density. With a reliable perturbation scheme Wertheim's renormalization procedure was applied. The resulting internal energy and pressure are compared with simulation results. An improved renormalized perturbation theory predicts thermodynamic properties in excellent to good agreement with simulation data.