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On the basis of a gaussian quasi-chemical model of hydration, a model of nonvan der Waals character, we explore the role of attractive methane-waterinteractions in the hydration of methane and in the potential of mean forcebetween two methane molecules in water. We find that the hydration of methaneis dominated by packing and a mean-field energetic contribution. Contributionsbeyond the mean-field term are unimportant in the hydration phenomena for ahydrophobic solute such as methane. Attractive solute-water interactions make anet repulsive contribution to these pair potentials of mean force. With noconditioning, the observed distributions of binding energies are super-gaussianand can be effectively modeled by a Gumbel (extreme value) distribution. Thisfurther supports the view that the characteristic form of the unconditioneddistribution in the high-e tail is due to energetic interactions with a smallnumber of molecules. Generalized extreme value distributions also effectivelymodel the results with minimal conditioning, but in those cases thedistributions are sufficiently narrow that details of their shape aren'tsignificant.

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