skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Covalent versus localized nature of 4 f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory

Abstract

We have conducted resonant angle-resolved photoemission spectroscopy of well-defined CeO 2 (111) and c – Ce 2 O 3 (111) model surfaces, revealing distinct f contributions in the valence band of the two compounds. In conjunction with density functional theory calculations, we show that the f contribution in CeO 2 is of a covalent nature, arising from hybridization with the O 2 p bands. In contrast, c – Ce 2 O 3 exhibits an almost nondispersive f state at 1.3 eV, which is indicative of almost negligible c-f hybridization.

Authors:
 [1];  [1];  [2];  [2];  [3];  [3];  [1];  [2];  [1]
  1. Charles Univ., Prague (Czech Republic). Faculty of Mathematics and Physics
  2. Hiroshima Univ., Hiroshima (Japan). Hiroshima Synchrotron Radiation Center
  3. Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1523840
Resource Type:
Journal Article
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 95; Journal Issue: 16; Journal ID: ISSN 2469-9950
Country of Publication:
United States
Language:
English

Citation Formats

Duchoň, Tomáš, Aulická, Marie, Schwier, Eike F., Iwasawa, Hideaki, Zhao, Chuanlin, Xu, Ye, Veltruská, Kateřina, Shimada, Kenya, and Matolín, Vladimír. Covalent versus localized nature of 4f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.95.165124.
Duchoň, Tomáš, Aulická, Marie, Schwier, Eike F., Iwasawa, Hideaki, Zhao, Chuanlin, Xu, Ye, Veltruská, Kateřina, Shimada, Kenya, & Matolín, Vladimír. Covalent versus localized nature of 4f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory. United States. doi:10.1103/PhysRevB.95.165124.
Duchoň, Tomáš, Aulická, Marie, Schwier, Eike F., Iwasawa, Hideaki, Zhao, Chuanlin, Xu, Ye, Veltruská, Kateřina, Shimada, Kenya, and Matolín, Vladimír. Sat . "Covalent versus localized nature of 4f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory". United States. doi:10.1103/PhysRevB.95.165124.
@article{osti_1523840,
title = {Covalent versus localized nature of 4f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory},
author = {Duchoň, Tomáš and Aulická, Marie and Schwier, Eike F. and Iwasawa, Hideaki and Zhao, Chuanlin and Xu, Ye and Veltruská, Kateřina and Shimada, Kenya and Matolín, Vladimír},
abstractNote = {We have conducted resonant angle-resolved photoemission spectroscopy of well-defined CeO 2 (111) and c – Ce 2 O 3 (111) model surfaces, revealing distinct f contributions in the valence band of the two compounds. In conjunction with density functional theory calculations, we show that the f contribution in CeO 2 is of a covalent nature, arising from hybridization with the O 2 p bands. In contrast, c – Ce 2 O 3 exhibits an almost nondispersive f state at 1.3 eV, which is indicative of almost negligible c-f hybridization.},
doi = {10.1103/PhysRevB.95.165124},
journal = {Physical Review B},
issn = {2469-9950},
number = 16,
volume = 95,
place = {United States},
year = {2017},
month = {4}
}

Works referenced in this record:

Empty f-states, Kondo insulators—or what?
journal, July 2001


Epitaxial Cubic Ce 2 O 3 Films via Ce–CeO 2 Interfacial Reaction
journal, March 2013

  • Stetsovych, Vitalii; Pagliuca, Federico; Dvořák, Filip
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1021/jz400187j

Nanoporous Gold-Supported Ceria for the Water–Gas Shift Reaction: UHV Inspired Design for Applied Catalysis
journal, July 2014

  • Shi, Junjie; Schaefer, Andreas; Wichmann, Andre
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp505433a

The electronic structure of CeO2 and PrO2
journal, July 1983


Counting electrons on supported nanoparticles
journal, December 2015

  • Lykhach, Yaroslava; Kozlov, Sergey M.; Skála, Tomáš
  • Nature Materials, Vol. 15, Issue 3
  • DOI: 10.1038/nmat4500

Covalent interactions in oxides
journal, June 2014


Probing bulk states of correlated electron systems by high-resolution resonance photoemission
journal, January 2000

  • Sekiyama, A.; Iwasaki, T.; Matsuda, K.
  • Nature, Vol. 403, Issue 6768
  • DOI: 10.1038/35000140

Spillover Reoxidation of Ceria Nanoparticles
journal, May 2016

  • Grinter, David C.; Muryn, Chris; Sala, Alessandro
  • The Journal of Physical Chemistry C, Vol. 120, Issue 20
  • DOI: 10.1021/acs.jpcc.6b03670

Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state
journal, January 2016


Mixed valency versus covalency in rare-earth core-electron spectroscopy
journal, February 1987


A resonant photoelectron spectroscopy study of Sn(Ox) doped CeO2 catalysts
journal, January 2008

  • Matolín, V.; Cabala, M.; Cháb, V.
  • Surface and Interface Analysis, Vol. 40, Issue 3-4
  • DOI: 10.1002/sia.2625

Multi-atom resonant photoemission
journal, March 2001

  • Kay, A. W.; Garcia de Abajo, F. J.; Yang, S. -H.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 114-116
  • DOI: 10.1016/S0368-2048(00)00429-1

Periodicity in the band gap variation of Ln2X3 (X = O, S, Se) in the lanthanide series
journal, September 1996


Covalent insulator CeO 2 : Optical reflectivity measurements
journal, July 1987


Ionic and covalent bonds in CeO2 crystal
journal, December 1995


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


The Binary Rare Earth Oxides
journal, June 1998

  • Adachi, Gin-ya; Imanaka, Nobuhito
  • Chemical Reviews, Vol. 98, Issue 4
  • DOI: 10.1021/cr940055h

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions
journal, January 2015

  • Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7097

Bulk modulus of CeO2 and PrO2—An experimental and theoretical study
journal, September 2005


Density functional study of CO on Rh(111)
journal, October 2004


Mixed-valent ground state of Ce O 2
journal, August 1983


Resonance photoemission studies of (111) oriented CeO2 thin film grown on Si (100) substrate by pulsed laser deposition
journal, November 2010

  • Khare, Amit; Choudhary, R. J.; Bapna, Komal
  • Journal of Applied Physics, Vol. 108, Issue 10
  • DOI: 10.1063/1.3514571

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Thermodynamic modelling of the cerium–oxygen system
journal, April 2006

  • Zinkevich, M.; Djurovic, D.; Aldinger, F.
  • Solid State Ionics, Vol. 177, Issue 11-12, p. 989-1001
  • DOI: 10.1016/j.ssi.2006.02.044

Ordered Phases of Reduced Ceria As Epitaxial Films on Cu(111)
journal, December 2013

  • Duchoň, Tomáš; Dvořák, Filip; Aulická, Marie
  • The Journal of Physical Chemistry C, Vol. 118, Issue 1
  • DOI: 10.1021/jp409220p

The interpretation of XPS spectra: Insights into materials properties
journal, June 2013


Nature of the electronic band gap in lanthanide oxides
journal, March 2013


Electron-spectroscopic manifestations of the 4f states in light rare-earth solids
journal, November 1985


Adsorption and Reaction of Methanol over CeO X (100) Thin Films
journal, March 2013

  • Albrecht, Peter M.; Mullins, David R.
  • Langmuir, Vol. 29, Issue 14
  • DOI: 10.1021/la400295f

Stability of the Ce 2 O 3 phases: A DFT + U investigation
journal, November 2007


Mixed valency in cerium oxide crystallographic phases: Valence of different cerium sites by the bond valence method
journal, April 2009


Spectroscopic Evidence for Localized and Extended f -Symmetry States in Ce O 2
journal, July 1984


X-ray absorption studies of CeO 2 , PrO 2 , and TbO 2 . I. Manifestation of localized and extended f states in the 3 d absorption spectra
journal, July 1987


Relationships between complex core level spectra and materials properties
journal, August 2010

  • Nelin, C. J.; Bagus, P. S.; Ilton, E. S.
  • International Journal of Quantum Chemistry, Vol. 110, Issue 15
  • DOI: 10.1002/qua.22807

Mixed valence: origins and developments
journal, September 2007

  • Day, Peter; Hush, Noel S.; Clark, Robin J. H.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 366, Issue 1862
  • DOI: 10.1098/rsta.2007.2135

Resonant photoemission study of CeO 2
journal, October 1994


Mixed-valence compounds
journal, April 1976


Absence of Ce 3+ Sites in Chemically Active Colloidal Ceria Nanoparticles
journal, November 2013

  • Cafun, Jean-Daniel; Kvashnina, Kristina O.; Casals, Eudald
  • ACS Nano, Vol. 7, Issue 12
  • DOI: 10.1021/nn403542p

Density functional theory study of flat and stepped NaCl(001)
journal, August 2007


Theoretical study of CeO2 and Ce2O3 using a screened hybrid density functional
journal, July 2006

  • Hay, P. Jeffrey; Martin, Richard L.; Uddin, Jamal
  • The Journal of Chemical Physics, Vol. 125, Issue 3
  • DOI: 10.1063/1.2206184