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 Plus monthly

Global: Zendy Tools annual

Global: Zendy Tools monthly

Global: Zendy Free Plan

How does an electrochemical interface respond to changes in the electrodepotential? How does the response affect the key properties of the system -energetics, excess charge, capacitance? Essential questions key to ab-initiosimulations of electrochemical systems, which we address in this work on thebasis of a rigorous mathematical evaluation of the interfacial energetics atconstant applied potential. By explicitly taking into account theconfigurational and electronic degrees of freedom we derive importantstatements about stationary points in the electronically grand canonicalensemble. We analyze their geometric response to changes in electrode potentialand show that it can be mapped identically onto an additional contribution tothe system's capacitance. We draw similar conclusions for the constant chargeensemble which equally allows to assess the respective stationary points. Ouranalysis of the relation between the canonical and grand canonical energeticsreveals, however, one key difference between both ensembles. While the constantpotential ensemble yields in general positive capacitances at local minima, thecapacitance of local minima in the constant charge ensemble might becomenegative. We trace back this feature to the possibility of character switchingof stationary points when switching between the ensembles causing thedifferences in the response to perturbations.  Our systematical analysis not only provides a detailed qualitative andquantitative understanding of the interplay between electronic andconfigurational degrees of freedom and their contributions to the energetics ofelectrified interfaces but also highlights the similarities and subtledissimilarities between the canonical and grand canonical description of theelectronic degrees of freedom, which is crucial for a better understanding oftheoretical calculations with and without potentiostat.

A Theoretical Investigation of the Grand- and the Canonical Potential  Energy Surface: The Interplay between Electronic and Geometric Response at  Electrified Interfaces