PNNL

Abstract

The covalent character of the interaction between the metal cation and the oxygen ligands has been examined for two Fe oxides with different nominal oxidation states, Fe(II)O and Fe(III)2O3. The covalent character is examined for the initial, ground state configuration and for the ionic states involving removal of a shallow core, Fe 3p, and a deep core, Fe 2p, electron. The covalency is assessed based on novel theoretical analyses of wavefunctions for the various cases. It is found that the covalency is considerably different for different oxidation states and for different ionized and non-ionized configurations. The changes in covalency for the ions are shown to be responsible for important changes in relaxation energies for X-Ray Photoelectron Spectroscopy, XPS, spectra and in the intensity lost from main XPS peaks to shake satellites. While these consequences are not observables themselves, they are important for the interpretation of the XPS spectra; in particular for efforts to extract stoichiometries of these iron oxides from XPS data. This is a finding likely applicable across various 3d transition metal oxide materials.