English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

We have used molecular simulation and methods of importance sampling to studythe thermodynamics and kinetics of ionic charge separation at a liquidwater-metal interface. We have considered this process using canonical examplesof two different classes of ions: a simple alkali-halide pair, Na$^+$I$^-$, orclassical ions, and the products of water autoionization, H$_3$O$^+$OH$^-$, orwater ions. We find that for both ion classes, the microscopic mechanism ofcharge separation, including water's collective role in the process, isconserved between the bulk liquid and the electrode interface. Despite this,the thermodynamic and kinetic details of the process differ between these twoenvironments in a way that depends on ion type. In the case of the classicalion pairs, a higher free energy barrier to charge separation and a smaller fluxover that barrier at the interface, results in a rate of dissociation that is40x slower relative to the bulk. For water ions, a slightly higher free energybarrier is offset by a higher flux over the barrier from longer lived hydrogenbonding patters at the interface, resulting in a rate of association that issimilar both at and away from the interface. We find that these differences inrates and stabilities of charge separation are due to the altered ability ofwater to solvate and reorganize in the vicinity of the metal interface.

Microscopic dynamics of charge separation at the aqueous electrochemical interface