[28] Furthermore, only reaction thermodynamics can be treated and kinetics need to be computed using other approaches. Because the electron and proton chemical potentials do not explicitly affect the DFT calculation, CHE cannot account for potential-and pH-dependent changes in the surface charge, electronic structure, and the mechanism, for instance. In particular, CHE assumes that the surface remains uncharged and thereby cannot account for surface charging effects or non-Nernstian effects arising from surface charge and dipole-field interactions. In the case of SCEs, neglecting the explicit surface charging effects means that CHE cannot be applied to study the impact of the SCR or polaronic and surface states as a function of the potential. The ensemble equivalence has been recently reaffirmed by numerical simulations, which show that the grand canonical and canonical ensembles converge in the infinite surface size limit. These works have also shown where N 0 e is the charge at a reference electrode potential, often chosen as the potential of zero charge, and μe is the change in the electrode potential with respect to this reference. Notably, the capacitance models provide an easy-to-apply and widely-applied electrochemical DFT approach but a good model for the capacitance as a function of potential is needed for accurate results. Because in the case of metallic electrodes the differential capacitance is mainly due to the electrolyte, a good model of the electrolyte capacitance has been deemed sufficient to successfully apply Eq. ( ) to metallic electrodes. However, when it comes to modeling SCEs, a good model for the electrolyte capacitance is not enough as the electrode itself significantly influences the capacitance. In particular, the total capacitance at the semiconductorelectrolyte interface (C SCE ) depends on both the semiconductor surface (C SC ) and the electrochemical double layer contributions (C DL ):