Koopmans' theorem

Directly relates experimental ionization potentials with energy levels of molecular orbitals. The theorem states that the ionization potential required to remove an electron from the orbital Ψ i is given by the negative value of the energy of the orbital, − ε i, as calculated within the Hartree–Fock approximation. The theorem is not applied to localized molecular orbitals, which are not eigenfunctions of the effective hamiltonian.
Source:
PAC, 1999, 71, 1919 (Glossary of terms used in theoretical organic chemistry) on page 1949