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

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.

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Abbreviations

DFT:

density functional theory

PBE:

Perdew–Burke–Ernzerhof

HSE06:

Heyd–Scuseria–Ernzerhof

FHI-aims:

Fritz–Haber Institute ab initio molecular simulations

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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.

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Correspondence to Juarez L. F. Da Silva.

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Ozório, M.S., Da Silva, A.C.H. & Da Silva, J.L.F. A Hybrid Density Functional Theory Investigation of the \(({\text {CeO}}_2)_{6}\) Clusters in the Cationic, Neutral, and Anionic States. J Clust Sci 31, 1213–1220 (2020). https://doi.org/10.1007/s10876-019-01728-z

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Keywords

  • Cerium oxide
  • Clusters
  • Density functional theory