Structure of the hydration shell of the Na+ ion in a planar nanopore with hydrophobic walls

The effect of steric hindrances in extremely narrow planar pores on the structure of the hydration shell of the single-charged sodium cation in water vapors at room temperature was studied by computer simulation. The deficiency of empty space for the motion in the slit-like pore was shown to slightly affect the radial distribution of molecules around the ion. The integrated (over the directions) numbers of ion-oxygen atom bonds of molecules in the ion’s hydration shell did not change despite the change in the shape of the hydration cluster from three- to two-dimensional. It was concluded that the changes in the positions of molecules relative to the ion were mainly reduced to azimuthal displacements; as a result, the local bulk density of molecules in the pore was higher than at the same distances outside the pore for the same total number of molecules. The distribution of molecules over layers inside the pore demonstrates the effect of molecules spread over the walls. The effect of ion displacement from its own hydration shell found earlier for the free chloride ion is steadily reproduced under the pore conditions. An alternative explanation to this effect was proposed that does not suggest high ion polarizability.