Role of attractive methane-water interactions in the potential of mean force between methane molecules in water

Abstract

On the basis of a Gaussian quasichemical model of hydration, a model of non-van der Waals character, we explore the role of attractive methane-water interactions in the hydration of methane and in the potential of mean force between two methane molecules in water. We find that the hydration of methane is dominated by packing and a mean-field energetic contribution. Contributions beyond the mean-field term are unimportant in the hydration phenomena for a hydrophobic solute such as methane. Attractive solute-water interactions make a net repulsive contribution to these pair potentials of mean force. With no conditioning, the observed distributions of binding energies are super-Gaussian and can be effectively modeled by a Gumbel (extreme value) distribution. This further supports the view that the characteristic form of the unconditioned distribution in the high-epsilon tail is due to energetic interactions with a small number of molecules. Generalized extreme value distributions also effectively model the results with minimal conditioning, but in those cases the distributions are sufficiently narrow that the details of their shape are not significant.