Density-Functional Calculations of the Structure of Near-Surface Oxygen Vacancies and Electron Localization on CeO2(111)

M. Verónica Ganduglia-Pirovano, Juarez L. F. Da Silva, and Joachim Sauer
Phys. Rev. Lett. 102, 026101 – Published 13 January 2009

Abstract

One of the most topical issues surrounding oxygen vacancies on CeO2(111) is the relative stability of surface and subsurface defects. Using density-functional theory (DFT) with the HSE06 (Heyd-Scuseria-Ernzerhof) hybrid functional as well as the DFT+U approach (where U is a Hubbard-like term describing the on-site Coulomb interactions), we find subsurface vacancies with (2×2) periodicity to be energetically more favorable by 0.45 (HSE06), 0.47 [PBE+U (Perdew-Burke-Ernzerhof functional)], and 0.22 eV [LDA+U (local density approximation)]. The excess electrons localize not on Ce ions which are the nearest neighbor to the defect as priorly suggested, but instead on those that are next-nearest neighbors. The excess-electron distribution and the preference for subsurface vacancies are explained in terms of defect-induced lattice relaxation effects.

  • Figure
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  • Received 29 May 2008

DOI:https://doi.org/10.1103/PhysRevLett.102.026101

©2009 American Physical Society

Authors & Affiliations

M. Verónica Ganduglia-Pirovano1,*, Juarez L. F. Da Silva1,2, and Joachim Sauer1

  • 1Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany
  • 2National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, Colorado 80401, USA

  • *Corresponding author. vgp@chemie.hu-berlin.de

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Vol. 102, Iss. 2 — 16 January 2009

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