Pressure Correction for Solvation Theories
arXiv:1908.10720 · doi:10.1063/5.0002029
Abstract
Liquid state theories such as integral equations and classical density functional theory often overestimate the bulk pressure of fluids because they require closure relations or truncations of functionals. Consequently, the cost to create a molecular cavity in the fluid is no longer negligible and those theories predict wrong solvation free energies. We show how to correct them simply by computing an optimized Van der Walls volume of the solute and removing the undue free energy to create such volume in the fluid. Given this versatile correction, we demonstrate that state-of-the-art solvation theories can predict, within seconds, hydration free energies of a benchmark of small neutral drug-like molecules with the same accuracy as day-long molecular simulations.
References in corpus (10)
- A nonequilibrium equality for free energy differences
- Statistically optimal analysis of samples from multiple equilibrium states
- Revised self-consistent continuum solvation in electronic-structure calculations
- Molecular Density Functional Theory of Water
- Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections
- Efficient molecular density functional theory using generalized spherical harmonics expansions
- Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models
- Solvation of complex surfaces via molecular density functional theory
- The Role of the Concentration Scale in the Definition of Transfer Free Energies
- Pressure Correction in Classical Density Functional Theory: Hyper Netted Chain and Hard Sphere Bridge Functionals