A molecular dynamics study on the role of attractive and repulsive forces in internal energy, internal pressure and structure of dense fluids

Isotherms of experimental data of internal pressure of dense fluids versus molar volume, Vm are shown to have each a maximum point at a Vmax below the critical molar volume. In this study, we investigated the role of attractive and repulsive intermolecular energies on this behavior using a molecular dynamics simulation technique. In the simulation, we choose the Lennard-Jones (LJ) intermolecular potential energy function. The LJ potential is known to be an effective potential representing a statistical average of the true pair and many-body interactions in simple molecular systems. The LJ potential function is divided into attractive and repulsive parts. MD calculations have produced internal energy, potential energy, transitional kinetic energy, and radial distribution function (RDF) for argon at 180 K and 450 K using LJ potential, LJ repulsive, and LJ attractive parts. It is shown that the LJ potential function is well capable of predicting the inflection point in the internal energy-molar volume curve as well as maximum point in the internal pressure-molar volume curve. It is also shown that at molar volumes higher than Vmax, the attractive forces have strong influence on determination of internal energy and internal pressure. At volumes lower than Vmax, neither repulsive nor attractive forces are dominating. Also, the coincidence between RDFs resulting from LJ potential and repulsive parts of LJ potential improves as molar volume approaches Vmax from high molar volumes. The coincidence becomes complete at Vmax ⩾ V.