Nonpolar solutes enhance water structure within hydration shells while reducing interactions between them

The origins of the hydrophobic effect are widely thought to lie in structural changes of the water molecules surrounding a nonpolar solute. The spatial distribution functions of the water molecules surrounding benzene and cyclohexane computed previously from molecular dynamics simulations show a high density first hydration shell surrounding both solutes. In addition, benzene showed a strong preference for hydrogen bonding with two water molecules, one to each face of the benzene ring. The position data alone, however, do not describe the majority of orientational changes in the water molecules in the first hydration shells surrounding these solutes. In this paper, we measure the changes in orientation of the water molecules with respect to the solute through spatial orientation functions as well as radial/angular distribution functions. These data show that the water molecules hydrogen bonded to benzene have a strong orientation preference, whereas those around cyclohexane show a weaker tendency. In addition, the water-water interactions within and between the first two hydration shells were measured as a function of distance and best hydrogen bonding angle. Water molecules within the first hydration shell have increased hydrogen bonding structure; water molecules interacting across shell 1 and shell 2 have reduced hydrogen bonding structure.