Simulation results and corresponding states correlation for pure rigid molecular fluids

Abstract

The compressibility, configurational internal and Helmholtz free energies, and the site-site and angle-averaged pair correlation functions are reported for six two-site and three-site Lennard-Jones molecules at a total of 212 state points computed by Monte Carlo simulation. This extensive data set can be used to test equations of state and statistical mechanical theories. A three-parameter corresponding states principle based on perturbed-hard-chain theory, using previously derived equations of state for the monatomic Lennard-Jones fluid, was used to correlate the simulation data with satisfactory accuracy. From the correlations and a simplified perturbation theory analysis, it is found that while the perturbed-hard-chain corresponding states method provides a reasonable correlation of the simulation data for small, rigid nonspherical molecules, the corresponding states parameters must have a different interpretation from the one usually given. Finally, the phase diagrams and critical properties of the mo...