Home > Research > Publications & Outputs > Field-dependent dehydration and optimal ionic e...

Associated organisational unit

Electronic data

  • output

    Accepted author manuscript, 16.5 MB, PDF document

    Available under license: CC BY: Creative Commons Attribution 4.0 International License

Links

Text available via DOI:

View graph of relations

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

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Published
<mark>Journal publication date</mark>1/07/2021
<mark>Journal</mark>Journal of Physical Chemistry B
Issue number25
Volume125
Number of pages16
Pages (from-to)7044-7059
Publication StatusPublished
Early online date11/06/21
<mark>Original language</mark>English

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.