Molecular Dynamics Simulations of Water Structure and Diffusion in a 1-nm-diameter Silica Nanopore as a Function of Surface Charge and Alkali Metal Counterion Identity

Abstract

Water confined in nanopores—particularly in pores narrower than 2 nm—displays distinct physicochemical properties that remain incompletely examined despite their importance in nanofluidics, molecular biology, geology, and materials sciences. Here, we use molecular dynamics simulations to investigate the coordination structure and mobility of water and alkali metals (Li, Na, K, Cs) inside a 1-nm-diameter cylindrical silica nanopore as a function of surface charge density, a model system particularly relevant to the alteration kinetics of silicate glasses and minerals in geologic formations. We find that the presence of negative surface charge and adsorbed counterions within the pore strongly impacts water structure and dynamics. In particular, it significantly orients water O-H bonds towards the surface and slows water diffusion by almost one order of magnitude. Ion crowding in the charged nanopore enhances the tendency of counterions to coordinate closely with the silica surface, which moderates the impact of ions on water dynamics. Co-ions are strongly excluded from the nanopore at all surface charges, suggesting that 1-nm-diameter cylindrical silica nanopores likely exhibit nearly ideal semi-permeable membrane transport properties.