Melting point and phase diagram of methanol as obtained from computer simulations of the OPLS model

Abstract

In this work, the melting point and the phase diagram of methanol is determined via computer simulations using the OPLS model. The three different solid structures that are found experimentally were considered. By computing the free energies of both the fluid phase and the three different solid structures (alpha, beta, gamma), the initial solid-solid and fluid-solid coexistence points were determined. By performing Gibbs-Duhem integration, the complete coexistence lines were evaluated. In this way, it was possible to compute, for the first time, the complete phase diagram for a potential model of methanol. It is found that the optimized potential model for liquid simulations (OPLS) provides reasonable predictions for the densities of the three solid polymorphs, although they tend to be somewhat low when compared with the experiment. Overall the model provides a qualitatively correct description of the phase diagram of methanol. The beta solid, which is thermodynamically stable in the experimental phase diagram of methanol, is found to be metastable in the phase diagram of the model. The alpha phase is stable at low pressures and the gamma phase is stable at high pressures, in agreement with experiment. Thus, the model is able to predict the existence of the gamma solid at high pressure. From free energy calculations we found that the melting point of the model at room pressure is 215 K. That was further confirmed by direct coexistence simulations. Thus, the model presents a melting point about 40 K above the experimental value of 175 K. Thus the OPLS model provides a reasonable description of the phase diagram of methanol, but it could probably be modified to improve the phase diagram predictions.