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Theoretical and numerical insight was gained into the relations between the Kohn-Sham orbital energies and relaxed vertical ionization potentials. A connection was made between the Kohn-Sham and Dyson one-electron theories. It was established that the energies of the occupied KS orbitals are distributed just like (minus) VIPs, which are the eigenvalues of the Dyson orbitals of the primary ionizations

the journal of chemical physics

Physical interpretation and evaluation of the Kohn–Sham and Dyson components of the ε–I relations between the Kohn–Sham orbital energies and the ionization potentials