Interplay of ion availability and mobility in the loss of cation selectivity for CaCl\textsubscript{2} in negatively charged nanopores: molecular dynamics using scaled-charge models

Abstract

Ion transport through charged nanopores is commonly interpreted in terms of electrical double layer structure, leading to the expectation of cation-selective conduction in negatively charged pores. This picture can break down for multivalent electrolytes, where strong ion-urface correlations and charge inversion modify transport behavior. Here, we study NaCl and CaCl${}_2$ conduction through negatively charged silica nanopores using atomistic molecular dynamics simulations with scaled-charge ion models. By separating concentration and velocity contributions to the radial particle current density, we connect static adsorption to dynamic perm-selectivity. While NaCl exhibits conventional cation selectivity, CaCl${}_2$ shows nearly bulk-like or even anion-favored transport due to Ca${}^{2+}$ immobilization near the surface and dominant Cl${}^{-}$ conduction in the pore interior following charge inversion. Although this qualitative mechanism is robust, its detailed manifestation depends sensitively on the balance of ion-surface and ion-water interactions encoded in the force field.

resubmitted to J. Chem. Phys. April 2026