CIP controls the inner potential and μbath e whereas constant E DF T f reflects the electrode potential inherent to the simulation cell (μ M e ) which for semiconducting materials does not equal to applied bath electrochemical potential. Consequently, we believe that the CIP-DFT method is more suitable than the E DF T f -based GCE-DFT for constant potential ab initio calculations of outer-sphere reactions and semiconductor electrodes.