Thermodynamic and Structural Evidence for Reduced Hydrogen Bonding among Water Molecules near Small Hydrophobic Solutes

The structure of water molecules near a hydrophobic solute remains elusive despite a long history of scrutiny. Here, we re-examine the subtle issue by a combination of thermodynamic analysis for Henry’s constants of several nonpolar gases over a broad range of temperatures and molecular dynamic simulations for the water structure in the hydration shell using several popular semiempirical models of liquid water. Both the structural and thermodynamic data indicate that hydrophobic hydration reduces the degree of the hydrogen bonding among water molecules, and the effect becomes more prominent at high temperatures. Hydrogen-bond formation is slightly hindered near a hydrophobic solute due to the restriction of the degree of freedom for water molecules in the solvation shell, and the confinement effect becomes more significant as temperature increases. Reduction in the extent of hydrogen bonding is fully consistent with a positive contribution of a small hydrophobic solute to the solution heat capacity. As predicted by the scaled-particle theory, both Henry’s constants and simulation results suggest that the hydration entropy is determined primarily by cavity formation in liquid water, with its magnitude rising with the solute size but declining with temperature