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Bipolar nanopores have powerful rectification properties due to the asymmetryin the charge pattern on the wall of the nanopore. In particular, bipolarnanopores have positive and negative surface charges along the pore axis.Rectification is strong if the radius of the nanopore is small compared to thescreening length of the electrolyte so that both cations and anions havedepletion zones in the respective regions. The depths of these depletion zonesis sensitive to sign of the external voltage. In this work, we are interestedin the effect of the presence of strong ionic correlations (both between ionsand between ions and surface charge) due to the presence of multivalent ionsand large surface charges. We show that strong ionic correlations cause leakageof the coions, a phenomenon that is absent in mean field theories. In thismodeling study, we use both the mean-field Poisson-Nernst-Planck (PNP) theoryand a particle simulation method, Local Equilibrium Monte Carlo (LEMC), to showthat phenomena such as overcharging and charge inversion cannot be reproducedwith PNP, while LEMC is able to produce nonmonotonic dependence of currents andrectification as a function of surface charge strength.

Rectification of bipolar nanopores in multivalent electrolytes: effect of charge inversion and strong ionic correlations