Ni 3s-hole states in NiO by non-orthogonal configuration interaction

The origin of the features in the Ni 3s X-ray photoelectron spectrum of NiO is investigated using a non-orthogonal configuration interaction approach for an embedded [NiO6] Cluster. We study the interplay of inter-atomic screening with the metal core hole and intra-atomic exchange and electron correlation effects. We show that the spectrum can be described in terms of only few key configurations, provided that orbital relaxation effects are explicitly taken into account for the excited charge transfer configurations. The strength of this approach has been demonstrated earlier for those final states that have a high-spin coupling. In the present contribution the analysis is extended to include low-spin coupled 3s-hole states. The effects of enlarging the embedded cluster and of an improved representation of the nearest cluster surroundings were studied for the high-spin final states. We found only minor effects on the computed peak separations. (c) 2006 Elsevier B.V. All rights reserved