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Title: Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2

Abstract

We report that 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, LnO2 (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 LnO2 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 LnO2, the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t2g (σ-bonding) and eg (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 a2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO2 that is ascribed to a unique interaction derived from the 4f orbitals of t1u symmetry (σ- and π-bonding). Lastly, O K-edge XAS and DFT resultsmore » are compared with complementary L3-edge and M5,4-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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2];  [3];  [2]; ORCiD logo [1];  [2];  [1]; ORCiD logo [4];  [1];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Colgate University, Hamilton, NY (United States)
  4. California State Polytechnic University, Pomona, CA (United States)
  5. Chinese Academy of Sciences, Taiyuan (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1485070
Grant/Contract Number:  
AC02-05CH11231; AC52-06NA25396; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 49; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, and Wen, Xiao-dong. Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2. United States: N. p., 2017. Web. doi:10.1021/jacs.7b10361.
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, & Wen, Xiao-dong. Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2. United States. doi:10.1021/jacs.7b10361.
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, and Wen, Xiao-dong. Tue . "Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2". United States. doi:10.1021/jacs.7b10361. https://www.osti.gov/servlets/purl/1485070.
@article{osti_1485070,
title = {Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2},
author = {Minasian, Stefan G. and Batista, Enrique R. and Booth, Corwin H. and Clark, David L. and Keith, Jason M. and Kozimor, Stosh A. and Lukens, Wayne W. and Martin, Richard L. and Shuh, David K. and Stieber, S. Chantal E. and Tylisczcak, Tolek and Wen, Xiao-dong},
abstractNote = {We report that 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, LnO2 (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 LnO2 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 LnO2, the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t2g (σ-bonding) and eg (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 a2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO2 that is ascribed to a unique interaction derived from the 4f orbitals of t1u symmetry (σ- and π-bonding). Lastly, O K-edge XAS and DFT results are compared with complementary L3-edge and M5,4-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.},
doi = {10.1021/jacs.7b10361},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 139,
place = {United States},
year = {2017},
month = {11}
}

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