Ionic Behavior in Highly Concentrated Aqueous Solutions Nanoconfined between Discretely Charged Silicon Surfaces

Abstract: Through molecular dynamics simulations considering thermal vibration of surface atoms, ionic behaviors in concentrated NaCl solutions confined between discretely charged silicon surfaces have been investigated. The electric double layer structure was found sensitive to the density and distribution of surface charges. Due to the surface charge discreteness, slight charge inversion appeared which depended on the surface charge density, bulk concentration and confinement. In the nanoconfined NaCl solutions differently concentrated from 0.2 M to 4.0 M, the locations of accumulation layers for Na+ and Cl- ions kept stable, but their peak values increased. The higher the concentration was, the more obvious charge inversion appeared. In 4.0 M NaCl solution, Na+ and Cl- ions show obvious alternating layered distributions which may be corresponding to the solidification found in experiments. By changing surface separation, the confinement had a large effect on ionic distributions. As both surfaces approached each other, many ions and water molecules were squeezed out of the confined space. Two adjacent layers in ion or water distribution profiles can be forced to closer to each other and merge together. From ionic hydration analysis, the coordination number of Na+ ions in highly-confined space was much lower than that in the bulk.