Anisotropic united-atoms (AUA) potential for alcohols.

ABSTRACT

An anisotropic united-atom (AUA4) intermolecular potential has been derived for the family of alkanols by first optimizing a set of charges to reproduce the electrostatic potential of the isolated molecules of methanol and ethanol and then by adjusting the parameters of the OH group to fit selected equilibrium properties. In particular, the proposed potential includes additional extra-atomic charges in order to improve the matching to the electrostatic field. Gibbs ensemble Monte Carlo simulations were performed to determine the phase equilibria, while the critical region was explored by means of grand canonical Monte Carlo simulations combined with histogram reweighting techniques. In order to increase the transferability of the model, only the parameters of the Lennard-Jones OH group have been fitted, the parameters of the other AUA groups are taken from previous works. Nevertheless, a good level of agreement was obtained for all compounds considered in this work. In particular, excellent results were obtained for the Henry constants calculation of different gases in alkanols.