Electronic structure and excitations in oxygen deficient CeO₂₋δ from DFT calculations

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The electronic structures of supercells of CeO₂₋δ have been calculated within the Density Functional Theory (DFT). The equilibrium properties such as lattice constants, bulk moduli and magnetic moments are well reproduced by the generalized gradient approximation (GGA). Electronic excitations are simulated by robust total energy calculations for constrained states with atomic core- or valence-holes. Pristine ceria CeO₂ is found to be a non-magnetic insulator with magnetism setting in as soon as oxygens are removed from the structure. In the ground state of defective ceria, the Ce-f majority band resides near the Fermi level, but appears at about 2 eV below the Fermi level in photoemission spectroscopy experiments due to final state effects. We also tested our computational method by calculating threshold energies in Ce-M₅ and O-K x-ray absorption spectroscopy and comparing theoretical predictions with the corresponding measurements. Our result that f electrons reside near the Fermi level in the ground state of oxygen deficient ceria is crucial for understanding catalytic properties of CeO₂ and related materials.