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Density functional study of oxygen vacancy formation and spin density distribution in octahedral ceria nanoparticles

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Abstract

We report plane wave basis density functional theory (DFT) calculations of the oxygen vacancies formation energy in nanocrystalline CeO 2-x in comparison with corresponding results for bulk and (111) CeO2 surface. Effects of strong electronic correlation of Ce4f states are taken into account through the use of an effective on-site Coulomb repulsive interaction within DFT+U approach. Different combinations of exchange-correlation functionals and corresponding U values reported in the literature are tested and the obtained results compared with experimental data. We found that both absolute values and trends in oxygen vacancy formation energy depend on the value of U and associated with degree of localization of Ce4f states. Effect of oxygen vacancy and geometry optimization method on spatial spin distribution in model ceria nanoparticles is also discussed.

Spin density in Ce44O80 nanocrystal reflects redistribution of localized f-electorns after the oxygen vacancy is introduced: all Ce cations at corner sites (except one) increase their magnetic moment to 0.97μB, while the edge opposite to the facet with vacancy has two Ce atoms with magnetic moment equal to 0.57μB, sharing f-electron.

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Acknowledgments

The research was supported in part by NSF (NIRT project CBET-0708172). The calculations were performed using (1) Stokes HPCC facility at UCF Institute for Simulation and Training (IST), (2) Bethe SMP server at UCF NanoScience Technology Center (NSTC), (3) the National Energy Research Scientific Computing Center (NERSC) , which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

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Authors and Affiliations

  1. NanoScience Technology Center, University of Central Florida, 12424 Research Parkway, Ste 400, Orlando, FL, 32826, USA

    Talgat M. Inerbaev, Sudipta Seal & Artëm E. Masunov

  2. Department of Mechanical, Material and Aerospace Engineering, University of Central Florida, 4000 Central Florida Blvd., Eng 381, Orlando, FL, 32816, USA

    Sudipta Seal

  3. Advanced Materials Processing and Analysis Center, University of Central Florida, 4000 Central Florida Blvd., Eng 381, Orlando, FL, 32816, USA

    Sudipta Seal

  4. Department of Chemistry, University of Central Florida, 4000 Central Florida Blvd., CH 117, Orlando, FL, 32816, USA

    Artëm E. Masunov

  5. Department of Physics, University of Central Florida, 4000 Central Florida Blvd., MAP 310, Orlando, FL, 32816, USA

    Artëm E. Masunov

  6. Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Orlando, FL, 32816, USA

    Artëm E. Masunov

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  1. Talgat M. Inerbaev
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  2. Sudipta Seal
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  3. Artëm E. Masunov
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Correspondence to Artëm E. Masunov.

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Inerbaev, T.M., Seal, S. & Masunov, A.E. Density functional study of oxygen vacancy formation and spin density distribution in octahedral ceria nanoparticles. J Mol Model 16, 1617–1623 (2010). https://doi.org/10.1007/s00894-010-0671-2

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  • DOI: https://doi.org/10.1007/s00894-010-0671-2

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