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

TL;DR

This study evaluates the accuracy of first-principles thermodynamic models in reproducing experimental cyclic voltammograms for Ag(100) electrodes in bromide solutions, highlighting the importance of solvation, field effects, and proper sampling.

Contribution

It demonstrates that combining implicit solvation, capacitive double layer corrections, and grand-canonical Monte Carlo yields accurate CV predictions, clarifying the impact of common approximations.

Findings

Implicit solvation and Monte Carlo methods improve CV accuracy.

Error cancellation can mask inadequate physics modeling.

Disorder-order transition of Br adlayer is crucial at higher coverages.

Abstract

Experimental cyclic voltammograms (CVs) measured in the slow scan rate limit can be entirely described in terms of thermodynamic equilibrium quantities of the electrified solid-liquid interface. They correspondingly serve as an important benchmark for the quality of first-principles calculations of the interfacial thermodynamics. Here, we investigate the partially drastic approximations made presently in computationally efficient such calculations for the well-defined showcase of a Ag(100) model electrode in Br-containing electrolytes, where the non-trivial 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, namely the potential-dependent adsorbate coverage and electrosorption valency, are derived from the first-principles energetics. We demonstrate that the combination of energetics obtained within an implicit solvation model and a perturbative second order account of capacitive double layer effects with a constant-potential grand-canonical Monte Carlo sampling of the adsorbate layer provides an accurate description of the experimental CV. However, our analysis also shows that error cancellation at lower levels of theory may equally lead to good descriptions even though key underlying physics like the disorder-order transition of the Br adlayer at increasing coverages is inadequately treated.