Interfacial Water at Hydrophobic and Hydrophilic Surfaces: Slip, Viscosity, and Diffusion

Abstract

The dynamics and structure of water at hydrophobic and hydrophilic diamond surfaces is examined via non-equilibrium Molecular Dynamics simulations. For hydrophobic surfaces under shearing conditions, the general hydrodynamic boundary condition involves a finite surface slip. The value of the slip length depends sensitively on the surface water interaction strength and the surface roughness; heuristic scaling relations between slip length, contact angle, and depletion layer thickness are proposed. Inert gas in the aqueous phase exhibits pronounced surface activity but only mildly increases the slip length. On polar hydrophilic surfaces, in contrast, slip is absent, but the water viscosity is found to be increased within a thin surface layer. The viscosity and the thickness of this surface layer depend on the density of polar surface groups. The dynamics of single water molecules in the surface layer exhibits a similar distinction: on hydrophobic surfaces the dynamics is purely diffusive, while close to a hydrophilic surface transient binding or trapping of water molecules over times of the order of hundreds of picoseconds occurs. We also discuss in detail the effect of the Lennard-Jones cutoff length on the interfacial properties.