New intermolecular potential models for benzene and cyclohexane

Abstract

New intermolecular potential models for benzene and cyclohexane have been developed, parameterized to the vapor–liquid coexistence properties. The models utilize the Buckingham exponential-6 potential to describe nonbonded interactions. Histograms reweighting grand canonical Monte Carlo methods were used to obtain the model parameters. A new algorithm for insertion of molecules with complex molecular architectures or stiff intramolecular constraints has been developed. The algorithm is based on the creation of a reservoir of ideal chains from which structures are selected for insertion during a simulation run. The new potential models reproduce the experimental saturated liquid densities and vapor pressures to within average absolute deviations of 0.3% and 2.2%, respectively. Critical parameters are also in good agreement with experiment. The infinite dilution behavior of these two cyclic molecules in water was studied. A combination of Widom insertion and expanded ensemble techniques were used to determine the Henry’s law constant of benzene and cyclohexane in water. The results obtained have qualitatively correct temperature dependence. However, the Henry’s constant of benzene in water is overestimated and that of cyclohexane is underestimated at all temperatures by approximately a factor of 3.