Molecular Realism in Default Models for Information Theories of Hydrophobic Effects

Abstract

This letter considers several physical arguments about contributions to hydrophobic hydration of inert gases, constructs default models to test them within information theories, and gives information theory predictions using those default models with moment information drawn from simulation of liquid water. Tested physical features include: packing or steric effects, the role of attractive forces that lower the solvent pressure, and the roughly tetrahedral coordination of water molecules in liquid water. Packing effects (hard sphere default model) and packing effects plus attractive forces (Lennard-Jones default model) are ineffective in improving the prediction of hydrophobic hydration free energies of inert gases over the previously used Gibbs and flat default models. However, a conceptually simple cluster Poisson model that incorporates tetrahedral coordination structure in the default model is one of the better performers for these predictions. These results provide a partial rationalization of the remarkable performance of the flat default model with two moments in previous applications. The cluster Poisson default model thus will be the subject of further refinement.