Theoretical studies of cohesive, electronic and redox properties of uranium dioxide

Abstract

Ionisation potentials calculated by Grant and Pyper are combined with calculations of lattice energy terms, in order to discuss the cohesive, spectroscopic and redox properties of UO₂. The results suggest first that the ionic model is a valid description of the bonding in this crystal. Secondly, an energy level diagram is proposed in which a narrow 5ƒ valence band lies above a broad oxygen 2p band. Our analysis of the thermodynamics of redox reactions supports previously proposed defect models.