X-ray photoelectron spectra and electronic structure of rare-earth orthovanadates

Photoelectron spectra of 4d and valence states in RVO₄ (R = Y, Nd, Eu, Gd, Tb, Dy, Yb) have been investigated. The experimental spectra are interpreted using the results of the Xα discrete variational method calculations for orthovanadates. Transformations of electronic structure and covalency in the RVO₄ series are discussed. It is shown that lanthanide 4f orbitals significantly mix with the O 2pAO's and hybridize with the rare-earths 5pAO's. The 5p levels spin-orbital splitting in orthovanadates has been evaluated.