Orbital Energies Are Chemical Potentials in Ground-State Density Functional Theory and Excited-State SCF Theory

We prove the general chemical potential theorem: the noninteracting one-electron orbital energies in DFT ground states and SCF excited states are corresponding chemical potentials of electron addition or removal, from an N-particle ground or excited state to an (N1) -particle ground or excited state. This greatly extends the previous ground state results. Combining with the recently developed exact linear conditions for fractional charges in excited states, where the slopes of the linear lines are defined as the excited-state chemical potentials, our result establish the physical meaning of orbital energies as approximation to the corresponding excited-state ionization potentials and electron affinities, for both ground and excited states of a molecule or a bulk system. To examine the quality of this approximation we demonstrate numerically significant delocalization error in commonly used functionals and excellent agreement in functionals correcting the delocalization error.