Loss for photoemission versus gain for Auger: Direct experimental evidence of crystal-field splitting and charge transfer in photoelectron spectroscopy

Abstract

Here, we find a 5 eV satellite in the Ti1s photoelectron spectrum of the transition-metal oxide SrTiO3. This satellite appears in addition to the well-studied 13 eV structure that is typically associated with the Ti2p core line. We give direct experimental evidence that the presence of two satellites is due to the crystal-field splitting of the metal 3d orbitals. They originate from ligand 2pt2g → metal3dt2g and ligand 2peg → metal 3deg monopole charge-transfer excitations within the sudden approximation of quantum mechanics. This assignment is made by the energetics of the resonant and high-energy threshold behaviors of the TiK–L2L3 Auger decay that follows Ti1s photoionization.