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The ability of semipermeable membranes to selectively impede the transport ofundesirable solutes is key to many applications. Yet, obtaining a systematicunderstanding of how membrane structure affects selectivity remains elusive dueto the insufficient spatiotemporal resolution of existing experimentaltechniques, and the inaccessibility of relevant solute transport timescales toconventional molecular simulations. Here, we utilize jumpy forward-fluxsampling to probe the transport of sodium and chloride ions through a graphiticmembrane with sub-nm pores. We find chlorides to traverse the pore at ratesover two orders of magnitude faster than sodiums. We also identify two majorimpediments to the transport of both ion types. In addition to the partialdehydration of the leading ion, its traversal induces charge anisotropy at itsrear, which exerts a net restraining force on the ion. Charge anisotropy istherefore a crucial hidden variable controlling the kinetics of ion transportthrough nanopores.

Induced Charge Anisotropy: a Hidden Variable Affecting Ion Transport through Membranes