Intermolecular Potentials of Methane Assessed by Second Virial Coefficients, ab Initio Dimer Interaction Energies, and Aggregate Cohesive Energies.

This study presents computations of three energy related properties for 26 previously published multisite intermolecular potentials of methane: MM2, MM3, MM2en, MM3en, MM2mc, MM3mc, MM3envir, RMK, OPLS all-atom, MUB-2, AMBER, BOYD, Williams, Sheikh, MG, Tsuzuki, E2-Gay, E4-Gay, MP4exp-6(iii), MP4exp-6(iv), Rowley-A, Rowley-B, TraPPE-EH, Ouyang, CLC, and Chao and three united atom potentials: Saager-Fischer (SF), OPLS united atom, and HFD. The three properties analyzed are the second virial coefficients for 14 temperature points in the range of 110 to 623.15 K, the interaction energies for 12 orientations of the methane dimer as a function of distance followed by a comparison to three ab initio data sets and the cohesive energy of the aggregate of 512 methane molecules. The latter computed energies are correlated to latent heat of evaporation of 11 potentials and are proposed as surrogate approximate parameters for ΔHvap for the studied potentials. The 10 best performing potentials are selected by rms order in each one of the properties and three of them are found to be present simultaneously in the three sets: Tsuzuki, MM3mc, and MM2mc. On the basis of the cohesive energy of the aggregate, a quantitative measure of the anisotropy of the potentials is proposed. The results are discussed on the basis of anisotropy, nonadditivity and ability of the potentials to reproduce ab initio data. It is concluded that the nonadditivity of the pair potentials holds and the available ab initio data did not lead to pair potentials that are cohesive enough to reproduce accurately the second virial coefficients.