Comparison of the Bulk and Surface Properties of Ceria and Zirconia by ab Initio Investigations
- 1 November 1999
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 103 (46), 10158-10170
- https://doi.org/10.1021/jp9913923
Abstract
In this paper, we present quantum mechanical (QM) calculations, at a periodic Hartee−Fock (HF) level, on the bulk and surface properties of cubic CeO2 and ZrO2. We have investigated the M−O bonding features, and established the high degree of ionicity of both materials, which is greater for CeO2 than ZrO2. The calculated values for the C11, C12, and C44 elastic constants, are in close agreement with experiment; an extended oxygen basis set, containing d-orbital polarization functions, is essential to model accurately the symmetry lowering during the C44 distortion. In the surface studies, we have calculated the surface energies of the {011} and {111} faces of both ceria and zirconia. QM results are compared with interatomic potential-based (IP) methods to assess the accuracy of the latter. We found that IP methods provide a correct estimate of the surface relaxations and the correct order of stability of the two faces examined, with the energy difference between the {011} and the {111} surfaces being approximately 1 J/m2, as in the QM study. However, IP methods do not always discriminate adequately between the properties of the two materials. Finally, we found that geometric and electronic relaxations in the {111} surface are confined to the outermost oxygen ions, while in the {011} slabs they are more important and extend to the subsurface layers in a columnar way. The unsaturation of the surface ions in the {011} face may have important implications for the catalytic activity of the materials.Keywords
This publication has 38 references indexed in Scilit:
- Defect cluster formation in M2O3-doped CeO2Solid State Ionics, 1999
- Oxygen Storage Dynamics in Pt/CeO2/Al2O3CatalystsJournal of Catalysis, 1998
- Defect Structure of NonstoichiometricSurfaces Studied by Scanning Tunneling MicroscopyPhysical Review Letters, 1997
- Energy-adjustedab initio pseudopotentials for the second and third row transition elements: Molecular test for M2 (M=Ag, Au) and MH (M=Ru, Os)Theoretical Chemistry Accounts, 1991
- Erratum: Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximationPhysical Review B, 1989
- Theoretical Estimates of Point Defect Energies in Cubic ZirconiaJournal of the American Ceramic Society, 1986
- Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitalsThe Journal of Chemical Physics, 1985
- Spectroscopic Evidence for Localized and Extended-Symmetry States in CePhysical Review Letters, 1984
- Special points for Brillouin-zone integrationsPhysical Review B, 1976
- Compressibilities of the Alkali MetalsThe Journal of Chemical Physics, 1938