Electronic structure and valence ionization energies of CrOCl3 studied by ab initio and SW-Xα methods

Abstract

The i.e.s of CrOCl₃ have been calculated by ab initio and SW-Xα methods. Ab initio calculations, both at the level of Koopmans' theorem and including orbital relaxation effects by the ΔSCF method, fail to predict the correct ground state of CrOCl⁺₃. The inclusion of limited correlation effects corrects this error as does a CI calculation which includes single excitations from the ionic configurations generated using the SCF m.o.s. of the ground state of CrOCl₃. A SW-Xα calculation using “muffin-tin” potentials also yields i.e.s in good agreement with the experimental photoelectron spectrum.