Molecular Density Functional Theory for water with liquid-gas coexistence and correct pressure

TL;DR

This paper introduces a bridge functional correction to molecular density functional theory that accounts for liquid-gas coexistence in water, enabling accurate predictions of hydration structures and energies of hydrophobic solutes.

Contribution

The authors propose a third order expansion of the functional to incorporate a metastable gas phase, improving thermodynamic consistency in water solvation models.

Findings

Accurately predicts hydration free energies of small solutes.

Reproduces macroscopic surface tension comparable to experiments.

Provides a computationally efficient alternative to empirical corrections.

Abstract

The solvation of hydrophobic solutes in water is special because liquid and gas are almost at coexistence. In the common hypernetted chain approximation to integral equations, or equivalently in the homogenous reference fluid of molecular density functional theory, coexistence is not taken into account. Hydration structures and energies of nanometer-scale hydrophobic solutes are thus incorrect. In this article, we propose a bridge functional that corrects this thermodynamic inconsistency by introducing a metastable gas phase for the homogeneous solvent. We show how this can be done by a third order expansion of the functional around the bulk liquid density that imposes the right pressure and the correct second order derivatives. Although this theory is not limited to water, we apply it to study hydrophobic solvation in water at room temperature and pressure and compare the results to all-atom simulations. With this correction, molecular density functional theory gives, at a modest computational cost, quantitative hydration free energies and structures of small molecular solutes like n-alkanes, and of hard sphere solutes whose radii range from angstroms to nanometers. The macroscopic liquid-gas surface tension predicted by the theory is comparable to experiments. This theory gives an alternative to the empirical hard sphere bridge correction used so far by several authors.