The 1s x-ray absorption pre-edge structures in transition metal oxides

Abstract

We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are calculated with the charge-transfer multiplet program. Tetrahedral coordination complexes have more intense pre-edge structures due to the local mixing of 3d and 4p states, implying a combination of 1s 3d quadrupole and 1s 4p dipole transitions. Divalent transition metal oxides can be described similar to coordination complexes, but for trivalent and tetravalent oxides, additional structures are visible in the pre-edge region due to non-local dipole transitions. The 1s 4p dipole transitions have large cross section at the 3d-band region due to the strong metal-metal interactions, which are oxygen mediated. This yields large intensity in the 3d-band region but at a different energy than the local 1s 3d quadrupole transitions because of smaller core-hole effects due to the delocalization of the excited electron.