Ab Initio-Based Modeling of Thermodynamic Cyclic Voltammograms: A Benchmark Study on Ag(100) in Bromide Solutions.

ABSTRACT: Experimental cyclic voltammograms (CVs) measured in the slow scan rate limit can be entirely described in terms of the thermodynamic equilibrium quantities of the electrified solid-liquid interface. They correspondingly serve as an important benchmark for the quality of first-principles calculations of interfacial thermodynamics. Here, we investigate the partially drastic approximations made presently in computationally efficient calculations for the well-defined showcase of an Ag(100) model electrode in Br-containing electrolytes, where the nontrivial part of the CV stems from the electrosorption of Br ions. We specifically study the entanglement of common approximations in the treatment of solvation and field effects, as well as in the way macroscopic averages of the two key quantities,

SUBMITTER: Bergmann N 

PROVIDER: S-EPMC10720351 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature