How Electrostatics Influences Hydrodynamic Boundary Conditions: Poiseuille and Electro-osmostic Flows in Clay Nanopores

We report on a molecular simulation study of the origin of nonslip or slip hydrodynamic boundary conditions in clay nanopores, focusing on the role of electrostatics. We simulate hydrodynamic and electro-osmotic flows and consider both charged (montmorillonite) and uncharged (pyrophyllite) clays. We further use two commonly used force fields to analyze the effect of local interactions, in particular, the effect of the polarity of the surface, in addition to the mere effect of the presence or absence of a net charge and counterions. For the 6 nm pore investigated here, the molecular velocity profile can be well described by continuum hydrodynamics only if (a) proper boundary conditions, with a slip or stagnation length determined from molecular simulation, are taken into account and (b) the ionic density profiles from MD simulations are used in the case of electro-osmotic flow, because the Poisson-Boltzmann equation fails to reproduce the ionic profiles, hence the force acting on the fluid. Among the considered force fields, only CLAYFF predicts a hydrophobic pyrophyllite and hydrophilic montmorillonite, as expected from experimental behavior. The nonslip or slip boundary conditions at clay surfaces strongly depend on electrostatic interactions of water molecules with the surface. The presence of a net charge results in an average electric field experienced by surface water molecules between the charged surface and the condensed layer counterions, which influences their orientation. The charge distribution inside the clay layer determines the polarity of the surface and hence the strength of hydrogen bonds donated by water molecules to surface oxygen atoms.