Fluids and fluid mixtures containing square-well diatomics: Equations of state and canonical molecular dynamics simulation

Abstract

We present new perturbation theory equations of state for square-well dimer fluids, square-well dimer mixtures, square-well dimer/monomer mixtures and square-well heteronuclear dumbbell fluids. Our first- and second-order perturbation terms are based on Barker and Henderson’s local compressibility approximation and Chang and Sandler’s perturbation theory, respectively. The perturbation approach requires knowledge of the radial distribution functions of the reference hard-dimer fluid and hard dimer/monomer mixture, which are obtained from molecular dynamics simulation. For mixtures we use one fluid mixing rules to approximate the average mixture structure and perturbation parameters. The predictions of the perturbation theory are compared to the compressibility factors obtained from discontinuous canonical molecular dynamics simulation, an adaptation of Anderson’s canonical ensemble molecular dynamics method to the case in which the potential is discontinuous.