A Predictive Molecular Orbital Theory Applied to Defects and Structures of Transition Metal Oxides
A quantum chemical approach for determining defect structures in cation-deficient transition metal monoxides is described. The method employs molecular orbital electronic energies for cations and anions in nearest-neighbor coordinations and adds to them interatomic pair-wise repulsion energies. Using this approach, zinc-blende structure extended defect clusters composed of 4:1 cluster building blocks are found to be most stable in Fe1-xO. These clusters account for the observed P′ and P″ phases in the iron oxide. The theory predicts that isolated cation vacancies with no clustering are most stable in Ni1-xO, in agreement with conductivity and diffusion data in the literature. For Co1-xO the experimental situation is unclear, and our theory suggests that small, but not extended, 4:1 defect clusters may form.
KeywordsCobaltous Oxide Internuclear Distance Defect Cluster Tetrahedral Interstice Bond Charge
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