Sub-Nanometer Interfacial Hydrodynamics: The Interplay of Interfacial Viscosity and Surface Friction

Abstract: For an accurate description of nanofluidic systems, it is crucial to account for the transport properties of liquids at surfaces on sub-nanometer scales, where classical hydrodynamics fails due to the finite range of surface-liquid interactions and modifications of the local viscosity. We show how to account for both via generalized, position-dependent surface-friction and interfacial viscosity profiles, which enables the accurate description of interfacial flow on the nanoscale using the Stokes equation. Such profiles are extracted from non-equilibrium molecular dynamics simulations of water on polar, non-polar, fluorinated, and unfluorinated alkane and alcohol self-assembled monolayers of widely varying wetting characteristics. Power-law relationships among the Navier friction coefficient, interfacial viscosity excess, and depletion length are revealed, and these are each found to be exponential in the work of adhesion. Our framework forms the basis for describing sub-nanometer fluid flow at interfaces with implications for electrokinetics, biophysics, and nanofluidics.