R. Zimmermann et al., STRONG HYBRIDIZATION IN VANADIUM-OXIDES - EVIDENCE FROM PHOTOEMISSIONAND ABSORPTION-SPECTROSCOPY, Journal of physics. Condensed matter, 10(25), 1998, pp. 5697-5716
We present x-ray photoemission spectra of the vanadium oxides V2O5, VO
2, and V2O3, and their analysis in terms of a simple cluster model bas
ed on the Anderson impurity Hamiltonian. The electronic structure of t
hese materials is characterized by a strong V 3d-O 2p hybridization en
ergy which exceeds the energy scales related to on-site Coulomb correl
ation and metal-ligand charge transfer. This result is at variance wit
h the usual Mon-Hubbard picture, but agrees with recent studies of oth
er early 3d transition metal compounds. The V 3d groundstate occupatio
ns obtained by the cluster-model analysis are considerably higher than
the values derived from the formal valencies. Covalency also affects
the exchange splitting observed in the V 3s core-hole spectra. X-ray a
bsorption measurements and resonant photoemission spectroscopy at the
V 2p-3d threshold provide further evidence for a strong V 3d-O 2p coup
ling.