Vapor–Liquid Coexistence Curves for Methanol and Methane Using Dispersion-Corrected Density Functional Theory.

First principles Monte Carlo simulations in the Gibbs and isobaric–isothermal ensembles were performed to map the vapor–liquid coexistence curves of methanol and methane described by Kohn–Sham density functional theory using the Becke–Lee–Yang–Parr (BLYP) exchange and correlation functionals with the Grimme correction term for dispersive (D2) interactions. The simulations indicate that the BLYP-D2 description with the TZV2P basis set underpredicts the saturated vapor densities and overpredicts the saturated liquid densities and critical and boiling temperatures for both compounds. Although the deviations are quite large, these results present a significant improvement over the BLYP functional without the correction term, which misses the experimental results by a larger extent in the opposite direction. Simulations at one temperature indicate that use of the larger QZV3P basis set may lead to improved saturated vapor densities, but not to significant changes in the liquid density. [ABSTRACT FROM AUTHOR]