Field-dependent dehydration and optimal ionic escape paths for C2N membranes

Barabash, Miraslau L. and Gibby, William A. T. and Guardiani, Carlo and Luchinsky, Dmitry G. and Luan, Binquan and Smolyanitsky, Alexander and McClintock, Peter V. E. (2021) Field-dependent dehydration and optimal ionic escape paths for C2N membranes. Journal of Physical Chemistry B, 125 (25). pp. 7044-7059. ISSN 1520-6106

Text (output)
output.pdf - Accepted Version
Available under License Creative Commons Attribution.
Download (17MB)

Abstract

Most analytic theories describing electrostatically-driven ion transport through water-filled nanopores assume that the corresponding permeation barriers are bias-independent. While this assumption may hold for sufficiently wide pores under infinitely small bias, transport through sub-nm pores under finite bias is difficult to interpret analytically. Given recent advances in sub-nm pore fabrication and the rapid progress in detailed computer simulations, it is important to identify and understand the specific field-induced phenomena arising during ion transport. Here we consider an atomistic model of electrostatically-driven ion permeation through subnanoporous C2N membranes. We analyse probability distributions of ionic escape trajectories and show that the optimal escape path switches between two different configurations, depending on bias magnitude. We identify two distinct mechanisms contributing to field-induced changes in transport-opposing barriers: a weak one arising from field-induced ion dehydration and a strong one due to the field-induced asymmetry of the hydration shells. The simulated current-voltage characteristics are compared with the solution of the 1D Nernst-Planck model. Finally, we show that the deviation of simulated currents from analytic estimates for large fields is consistent with the field-induced barriers and the observed changes in the optimal ion escape path.