Vapor Liquid Equilibria of Hydrofluoromethanes Via First Principles Monte Carlo Simulations

The Kohn-Sham density functional theory (DFT)  is a popular approach to compute condensed phase properties. In Kohn-Sham DFT, the local or semi local density functionals do not  capture van der Waals interactions accurately. An accurate description of van der Waals interactions is essential in determing  thermodyanmic properties of molecules. The development of fully non local van der Waals density functional adequatey describe dispersion interactions.  In this work, we present first principles Monte Carlo simulations to obtain vapor liquid coexistence curves for hydrofluorocarbons (CF₄, CF₃H, CF₂H₂, CH₃F) by using Becke-Lee-Yang-Parr (BLYP) and Perdew-Burke-Ernzerhof (PBE) functional with dispersion corrected models and rVV10 nonlocal van der Waals density functional.  This work is of prime importance to predict phase equilibria, thermophysical properties, critical properties and structural properties for hydrofluorocarbons directly from first principles calculations.