Density Depletion and Enhanced Fluctuations in Water near Hydrophobic Solutes: Identifying the Underlying Physics.

We investigate the origin of the density depletion and enhanced density fluctuations that occur in water in the vicinity of an extended hydrophobic solute. We argue that both phenomena are remnants of the critical drying surface phase transition that occurs at liquid-vapor coexistence in the macroscopic planar limit, i.e., as the solute radius R_{s}→∞. Focusing on the density profile ρ(r) and a sensitive spatial measure of fluctuations, the local compressibility profile χ(r), we develop a scaling theory which expresses the extent of the density depletion and enhancement in compressibility in terms of R_{s}, the strength of solute-water attraction ϵ_{s}, and the deviation from liquid-vapor coexistence δμ. Testing the predictions against results of classical density functional theory for a simple solvent and grand canonical Monte Carlo simulations of a popular water model, we find that the theory provides a firm physical basis for understanding how water behaves at a hydrophobe.