Static and dynamic correlations in water near hydrophobic interfaces

PHYS 158

Jeetain Mittal,, Laboratory of Chemical Physics, National Institutes of Health, Bldg. 5, Room 114, Bethesda, MD 20892-0520 and Gerhard Hummer,, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892-0520.
Water behavior near large hydrophobic solutes and extended surfaces is markedly different from that near small solutes and in the bulk. We discuss recent results from extensive molecular simulations of TIP4P water near purely repulsive and weakly attractive solute particles. We find that the observed structure of the solute-water interface is consistent with capillary-wave induced broadening. The interfacial tension calculated using capillary-wave theory is in close agreement with the surface tension of water-vapor interface for the TIP4P water model. We characterize the structural and dynamical correlations in water near a dry interface and as a function of water-solute interaction strength, including regimes at negative pressure. Finally, we discuss implications of our results for self-assembly processes in the vicinity of a dewetted surface.