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

Using the example of a proton adsorption process, we analyze and compare two prominent modeling approaches in computational electrochemistry at metallic electrodes─electronically canonical, constant-charge and electronically grand-canonical, constant-potential calculations. We first confirm that both methodologies yield consistent results for the differential free energy change in the infinite cell size limit. This validation emphasizes that, fundamentally, both methods are equally valid and precise. In practice, the grand-canonical, constant-potential approach shows superior interpretability and size convergence as it aligns closer to experimental ensembles and exhibits smaller finite-size effects. On the other hand, constant-charge calculations exhibit greater resilience against discrepancies, such as deviations in interfacial capacitance and absolute potential alignment, as their results inherently only depend on the surface charge and not on the modeled charge vs potential relation. The present analysis thus offers valuable insights and guidance for selecting the most appropriate ensemble when addressing diverse electrochemical challenges.