Molecular origin of the hydrophobic effect: analysis using the angle-dependent integral equation theory.

The molecular origin of the hydrophobic effect is investigated using the angle-dependent integral equation theory combined with the multipolar water model. The thermodynamic quantities of solvation (excess quantities) of a nonpolar solute are decomposed into the translational and orientational contributions. The translational contributions are substantially larger with the result that the temperature dependence of the solute solubility, for example, can well be reproduced by a model simple fluid where the particles interact through strongly attractive potential such as water and the particle size is as small as that of water. The thermodynamic quantities of solvation for carbon tetrachloride, whose molecular size is approximately 1.9 times larger than that of water, are roughly an order of magnitude smaller than those for water and extremely insensitive to the strength of solvent-solvent attractive interaction and the temperature. The orientational contributions to the solvation energy and entropy are further decomposed into the solute-water pair correlation terms and the solute-water-water triplet and higher-order correlation terms. It is argued that the formation of highly ordered structure arising from the enhanced hydrogen bonding does not occur in the vicinity of the solute. Our proposition is that the hydrophobic effect is ascribed to the interplay of the exceptionally small molecular size and the strongly attractive interaction of water, and not necessarily to its hydrogen-bonding properties.