Interfacial properties of binary mixtures of Lennard-Jones chains in planar interfaces by molecular dynamics simulation

Abstract

Binary mixtures of fully flexible linear tangent chains composed of bonded Lennard-Jones interaction sites (monomers) were studied using the molecular dynamics simulation in the NVT ensemble. Their interfacial properties were investigated in planar interfaces by direct simulation of an explicit liquid film in equilibrium with its vapor. A method for the calculation of long-range interactions in inhomogeneous fluids was implemented to take into account the potential truncation effects. Surface tension and the pressure tensor were calculated via the classical Irving-Kirkwood method; vapor pressure, orthobaric densities, density profiles, and Gibbs relative adsorption of the volatile component with respect to the heavy component were also obtained. The properties were studied as a function of the temperature, molar concentration of the heavy component, and the asymmetry of the mixture. According to the results of this work, the temperature loses influence on the surface tension, vapor pressure, and Gibbs relative adsorption curves as the molecular length of the heavy component increases. This suggests that the universal behavior observed in pure fluids of Lennard-Jones chains also holds for binary mixtures. The contribution of the long-range interactions turned out to account for about 60%, 20%, and 10% of the surface tension, vapor pressure, and orthobaric density final values, respectively. This contribution was even larger at high temperatures and for large molecules. Strong enrichment of the volatile component at the interface was observed in the asymmetric mixtures. One of these mixtures even showed a barotropic effect at elevated pressures and a class III phase behavior.