The discussion above holds for both metallic and semiconducting (SC) electrodes, and even the presence of Schottky barrier between the metallic contact and the SC electrode does not changes the picture:μ M e = μbath e = E F condition must remain at equilibrium. However, the finite number of charge carriers or dopants, their spatial dopant concentrations, and their effect on the electrostatics in semiconductors have to be considered. When all of these are accounted for, the semiconductor Fermi level, E SC f , is defined to reside within a band gap and can always be converted to an experimental scale through Eq. (2) after choosing a suitable reference for K. In practice, DFT simulations of semiconductor electrodes introduce further points to consider for GCE-DFT calculations.