Density-functional calculation of CeO 2 surfaces and prediction of effects of oxygen partial pressure and temperature on stabilities

Yong Jiang, James Adams, Mark Van Schilfgaarde

Research output: Contribution to journalArticle

143 Citations (Scopus)

Abstract

We have used density-functional theory to investigate (111), (110), (210), (211), (100), and (310) surfaces of ceria (Ce O2). Compared with previous interatomic-potential-based studies, our calculations reported a slightly different relative stability ordering and significantly lower surface energies for the stoichiometric surfaces. Using a defect model, the surface stabilities were evaluated as functions of oxygen partial pressure and temperature. Our investigations were restricted to ideal surface terminations, without considering defect formation on those surfaces. We found that at 300 K, the stoichiometric (111) has the lowest free energy for a wide range of oxygen partial pressures up to 1 atm, and only at ultrahigh vacuum does the Ce-terminated (111) becomes the most stable one. The transition point for the Ce-terminated (111) surfaces moves to higher oxygen partial pressures when temperature increases. To improve the prediction of electron density of states, we used the local-density approximation plus U (J) correction method to correct the on-site Coulomb correlation and exchange interaction due to the strongly localized Ce-4f electrons. The optimal parameter combination of U=7 eV and J=0.7 eV was found to improve the O 2p-Ce 4f gap without much degradation of ground-state bulk properties or the O 2p-Ce 5d gap. The bulk and surface electronic structures were then analyzed based on the improved density of states.

Original languageEnglish (US)
Article number064701
JournalJournal of Chemical Physics
Volume123
Issue number6
DOIs
StatePublished - Aug 8 2005

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Partial pressure
Density functional theory
partial pressure
Oxygen
oxygen
predictions
Temperature
temperature
surface stability
defects
Local density approximation
Defects
transition points
Electronic density of states
Exchange interactions
Cerium compounds
Ultrahigh vacuum
ultrahigh vacuum
surface energy
Interfacial energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Density-functional calculation of CeO 2 surfaces and prediction of effects of oxygen partial pressure and temperature on stabilities. / Jiang, Yong; Adams, James; Van Schilfgaarde, Mark.

In: Journal of Chemical Physics, Vol. 123, No. 6, 064701, 08.08.2005.

Research output: Contribution to journalArticle

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