Dissecting Hydrophobic Hydration and Association

Abstract

We use appropriately defined short ranged reference models of liquid water to clarify the different roles local hydrogen bonding, van der Waals attractions, and long ranged electrostatic interactions play in the solvation and association of apolar solutes in water. While local hydrogen bonding in- teractions dominate hydrophobic effects involving small solutes, longer ranged electrostatic and dis- persion interactions are found to be increasingly important in the description of interfacial structure around large solutes. The hydrogen bond network sets the solute length scale at which a crossover in solvation behavior between these small and large length scale regimes is observed. Unbalanced long ranged forces acting on interfacial water molecules are also important in hydrophobic association, illustrated here by analysis of the association of model methane and buckminsterfullerene solutes.

14 pages

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Cited by in corpus (9)

• Ab initio theory and modeling of water
• The molecular structure of the interface between water and a hydrophobic substrate is liquid-vapor like
• Pathways to dewetting in hydrophobic confinement
• Understanding Hydrophobic Effects: Insights from Water Density Fluctuations
• Water Density Fluctuations Relevant to Hydrophobic Hydration are Unaltered by Attractions
• Solvent-mediated interactions between nanostructures: from water to Lennard-Jones liquid
• Exponential Scaling of Water Exchange Rates with Ion Interaction Strength from the Perspective of Dynamic Facilitation Theory
• Learning intermolecular forces at liquid-vapor interfaces
• Characterizing Solvent Density Fluctuations in Dynamical Observation Volumes