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A Hybrid Density Functional Theory Investigation of the \(({\text {CeO}}_2)_{6}\) Clusters in the Cationic, Neutral, and Anionic States

  • Mailde S. Ozório
  • Augusto C. H. Da Silva
  • Juarez L. F. Da SilvaEmail author
Original Paper
  • 39 Downloads

Abstract

We report a quantum-chemistry investigation of the cationic, neutral, and anionic \(({\text {CeO}}_2)_{6}\) clusters to obtain an atom-level understanding of the effects induced by the release or addition of a single electron on the physical and chemical properties of small oxide clusters. Our ab initio calculations are based on density functional theory (DFT) within the hybrid Heyd–Scuseria–Ernzerhof (HSE06) and semilocal Perdew–Burke–Ernzerhof (PBE) functional. Compared with PBE, the HSE06 functional changes the relative stability of the neutral \(({\text {CeO}}_2)_{6}\) isomers, in particular, for structures with small total energy differences, e.g., about \(100 \, \text {meV/fu}\), which can be explained by the enhancement of the exchange interactions. The addition of an electron to the \(({\text {CeO}}_2)_{6}\) clusters change the oxidation state of a single \(\text {Ce}\) atom from + IV to + III, which drives a local distortion and the formation of a small polaron near to the \({\text {Ce}}^{\text{III}}\) cation. In contrast, the release of an electron induces the formation of a localized hole on one of the \(\text {O}\) atoms combined with local structural distortions. For the anionic and cationic clusters in the putative global minimum configurations, we found a strain energy induced by the distortion of 1.00 and 1.31 eV, respectively.

Keywords

Cerium oxide Clusters Density functional theory 

Abbreviations

DFT

density functional theory

PBE

Perdew–Burke–Ernzerhof

HSE06

Heyd–Scuseria–Ernzerhof

FHI-aims

Fritz–Haber Institute ab initio molecular simulations

Notes

Acknowledgements

The authors gratefully acknowledge support from FAPESP (São Paulo Research Foundation, Grant Number 2017/11631-2), Shell and the strategic importance of the support given by ANP (Brazils National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation. This study was financed in part by the National Counsel of Technological and Scientific Development (fellowships for Mailde S. Ozório and Augusto C. H. Da Silva). The authors acknowledge also the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil) for providing HPC resources of the SDumont supercomputer, which have contributed to the research results reported within this paper. http://sdumont.lncc.br. We acknowledges also the Advanced Scientific Computational Laboratory (University of São Paulo) and the infrastructure provided to our computer cluster by the São Carlos Center of Informatics, University of São Paulo.

Supplementary material

10876_2019_1728_MOESM1_ESM.pdf (15.5 mb)
Supplementary material 1 (PDF 154 kb)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Mailde S. Ozório
    • 1
  • Augusto C. H. Da Silva
    • 1
  • Juarez L. F. Da Silva
    • 1
    Email author
  1. 1.São Carlos Institute of ChemistryUniversity of São PauloSão CarlosBrazil

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