Rapid prediction of solvation free energy and vapor pressure of liquid and solid from molecular dynamics simulation

Abstract

We show that the solvation free energy and vapor pressure, important thermodynamic properties of pure substances in liquid or solid states, can be obtained from short, about 20 ps, molecular dynamics simulations. The method combines the determination of free energy of a chemical in vacuum using the normal‐mode analysis (NMA, energy minimization), and in the condensed phase using the two‐phase thermodynamic (2PT) model. We have examined the calculation results for common liquids and solids, including water, alcohol, acid, aromatics, and alkanes. The results, referred to as 2PT‐NMA, is comparable to those calculated from thermodynamic integration (TI) for liquids, and is readily applicable to solids, where simple TI is not applicable. Furthermore, the free energy from 2PT‐NMA converges (20 ps) much faster than that from TI (1 ns). The new method could be a very useful tool for fast screening of condensed phase pressure from the trajectory of MD simulations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2298–2306, 2015