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Experimental cyclic voltammograms (CVs) measured in the slow scan rate limitcan be entirely described in terms of thermodynamic equilibrium quantities ofthe electrified solid-liquid interface. They correspondingly serve as animportant benchmark for the quality of first-principles calculations of theinterfacial thermodynamics. Here, we investigate the partially drasticapproximations made presently in computationally efficient such calculationsfor the well-defined showcase of a Ag(100) model electrode in Br-containingelectrolytes, where the non-trivial part of the CV stems from theelectrosorption of Br ions. We specifically study the entanglement of commonapproximations in the treatment of solvation and field effects, as well as inthe way macroscopic averages of the two key quantities, namely thepotential-dependent adsorbate coverage and electrosorption valency, are derivedfrom the first-principles energetics. We demonstrate that the combination ofenergetics obtained within an implicit solvation model and a perturbativesecond order account of capacitive double layer effects with aconstant-potential grand-canonical Monte Carlo sampling of the adsorbate layerprovides an accurate description of the experimental CV. However, our analysisalso shows that error cancellation at lower levels of theory may equally leadto good descriptions even though key underlying physics like the disorder-ordertransition of the Br adlayer at increasing coverages is inadequately treated.

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