An intermolecular potential for hydrogen: Classical molecular simulation of pressure–density–temperature behavior, vapor–liquid equilibria, and critical and triple point properties

Abstract

An intermolecular potential is reported for molecular hydrogen that combines two-body interactions from ab initio data with three-body interactions. The accuracy of the two-body potential is validated by comparison with experimental second virial coefficient data. Experimental pressure–density–temperature data are used to validate the addition of three-body interactions, often yielding very accurate predictions. Classical Monte Carlo simulations that neglect quantum effects are reported for the vapor–liquid equilibria (VLE), critical properties, and the triple point. A comparison with experimental data indicates that the effect of quantum interactions is to narrow the VLE phase envelope and to lower the critical temperature. The three-body interactions have a considerable influence on the phase behavior, resulting in good agreement with the experimental density. The critical properties of the two-body + three-body potential for hydrogen provide an alternative set of input parameters to improve the accuracy of theoretical predictions at temperatures above 100 K. In the vicinity of the critical point, the coexistence densities do not obey the law of rectilinear diameters, which is a feature that has largely been overlooked in both experimental data and reference equations of state.