Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

By Georg Kastlunger, Per G Lindgren, Andrew A. Peterson. Journal of Physical Chemistry C, 2018

196 citations recorded by the source corpus.

The simulation of electrochemical reaction dynamics from first principles remains challenging, since over the course of an elementary step, an electron is either consumed or produced by the electrode. For example, the hydrogen evolution reaction begins with a simple proton discharge to a metal surface, but with conventional electronic structure methods, the simulated potential, which is manifested as the metal’s workfunction, varies over the course of the simulation as the electron is consumed in the new metal–hydrogen bond. Here, we present a simple approach to allow the direct control of the electrochemical potential via charging of the electrode surface. This is achieved by changing the total number of electrons in the self-consistent cycle, while enforcing charge neutrality through the introduction of a jellium counter charge dispersed in an implicit solvent region above the slab. We observe that the excess electrons localize selectively at the metal’s reactive surface and that the metal workfunction ...

Subfields: Electrochemistry, Renewable Energy, Sustainability and the Environment

View Paper: https://www.semanticscholar.org/paper/2b7115c4e7cefffd7fbd8e033b407d6db4097429