Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO, PrO, and TbO.
Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides...
| Published in: | Journal of the American Chemical Society Vol. 139; no. 49; pp. 18052 - 18065 |
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| Main Authors: | , , , , , , , , , , , |
| Format: | Article |
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American Chemical Society
12/13/2017
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=126761885&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 126761885 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/13/2017 vid: 139 iid: 49 pid: 997 pub: American Chemical Society artinfo: ui: 126761885 10.1021/jacs.7b10361 ppf: 18052 ppct: 13 formats: tig: atl: Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO, PrO, and TbO. aug: au: Minasian, Stefan G. Batista, Enrique R. Booth, Corwin H. Clark, David L. Keith, Jason M. Kozimor, Stosh A. Lukens, Wayne W. Martin, Richard L. Shuh, David K. Stieber, S. Chantal E. Tylisczcak, Tolek Xiao-dong Wen affil: Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States Colgate University, Hamilton, New York 13346, United States California State Polytechnic University, Pomona, California 91768, United States Chinese Academy of Sciences, Taiyuan 030032, China su: Rare earth metals Molecular orbitals Cerium oxides Terbium Praseodymium Quantitative research Density functional theory X-ray absorption spectra sug: subj: Rare earth metals Molecular orbitals Cerium oxides Terbium Praseodymium Quantitative research Density functional theory X-ray absorption spectra ab: Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO, the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t (σ-bonding) and e (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO that is ascribed to a unique interaction derived from the 4f orbitals of t symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L-edge and M-edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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