Induced Charge Anisotropy: a Hidden Variable Affecting Ion Transport through Membranes (1906.00853v2)

Abstract: The ability of semipermeable membranes to selectively impede the transport of undesirable solutes is key to many applications. Yet, obtaining a systematic understanding of how membrane structure affects selectivity remains elusive due to the insufficient spatiotemporal resolution of existing experimental techniques, and the inaccessibility of relevant solute transport timescales to conventional molecular simulations. Here, we utilize jumpy forward-flux sampling to probe the transport of sodium and chloride ions through a graphitic membrane with sub-nm pores. We find chlorides to traverse the pore at rates over two orders of magnitude faster than sodiums. We also identify two major impediments to the transport of both ion types. In addition to the partial dehydration of the leading ion, its traversal induces charge anisotropy at its rear, which exerts a net restraining force on the ion. Charge anisotropy is therefore a crucial hidden variable controlling the kinetics of ion transport through nanopores.