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Journal of Chemical Physics / Volume 136 / Issue 4 / COMMUNICATIONS
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J. Chem. Phys. 136, 041101 (2012); http://dx.doi.org/10.1063/1.3678309 (4 pages)

Communication: Improving the density functional theory+U description of CeO2 by including the contribution of the O 2p electrons

José J. Plata, Antonio M. Márquez, and Javier Fdez. Sanz

Departamento de Química Física, Facultad de Química, Universidad de Sevilla, 41012 Sevilla, Spain

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(Received 7 November 2011; accepted 3 January 2012; published online 23 January 2012)

Density functional theory (DFT) based approaches within the local-density approximation or generalized gradient approximation frameworks fail to predict the correct electron localization in strongly correlated systems due to the lack of cancellation of the Coulomb self-interaction. This problem might be circumvented either by using hybrid functionals or by introducing a Hubbard-like term to account for the on site interactions. This latter DFT+U approach is less expensive and therefore more practical for extensive calculations in solid-state computational simulations. By and large, the U term only affects the metal electrons, in our case the Ce 4f ones. In the present work, we report a systematic analysis of the effect of adding such a U term also to the oxygen 2p electrons. We find that using a set of Uf = 5 eV and Up = 5eV effective terms leads to improved description of the lattice parameters, band gaps, and formation and reduction energies of CeO2.

© 2012 American Institute of Physics

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KEYWORDS and PACS

Keywords

cerium compounds, density functional theory, energy gap, lattice constants, strongly correlated electron systems

PACS

  • 71.20.Ps

    Other inorganic compounds

  • 71.27.+a

    Strongly correlated electron systems; heavy fermions

  • 61.66.Fn

    Inorganic compounds

  • 71.15.Mb

    Density functional theory, local density approximation, gradient and other corrections

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3678309

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (4) Tables (2)

Figures (click on thumbnails to view enlargements)

FIG.1
Dependency of the CeO2 lattice parameter, a0, on the Uf and Up values.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
Total density of states (DOS) for CeO2 with the definition of the band gaps. Obtained with the (5+5) set.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
Dependency of the CeO2 band gaps on the Uf and Up values.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.4
Electron spin density of bulk CeO2 after removing an oxygen atom showing the formation of two CeIII centers localized around the vacancy.

FIG.4 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Tables

Table I. Calculated and experimental lattice parameters (in Å) for CeO2 and Ce2O3.

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Table II. Energy (eV) of CeO2 formation and its reduction: CeO2 → Ce2O3 + 1/2 O2.

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