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Using the example of a proton adsorption process, we analyze and compare twoprominent modelling approaches in computational electrochemistry at metallicelectrodes - electronically canonical, constant-charge and electronicallygrand-canonical, constant-potential calculations. We first confirm that bothmethodologies yield consistent results for the differential free energy changein the infinite cell size limit. This validation emphasizes that,fundamentally, both methods are equally valid and precise. In practice, thegrand-canonical, constant-potential approach shows superior interpretabilityand size convergence as it aligns closer to experimental ensembles and exhibitssmaller finite-size effects. On the other hand, constant-charge calculationsexhibit greater resilience against discrepancies, such as deviations ininterfacial capacitance and absolute potential alignment, as their resultsinherently only depend on the surface charge, and not on the modelled chargevs. potential relation. The present analysis thus offers valuable insights andguidance for selecting the most appropriate ensemble when addressing diverseelectrochemical challenges.

Converging Divergent Paths: Constant Charge vs. Constant Potential Energetics in Computational Electrochemistry