Comparative Study on the Performance of Hybrid DFT Functionals in Highly Correlated Oxides: The Case of CeO2 and Ce2O3

• Published in: Journal of chemical theory and computation Vol. 7; no. 1; pp. 56 - 65
• Main Authors: Graciani, Jesús, Márquez, Antonio M, Plata, José J, Ortega, Yanaris, Hernández, Norge C, Meyer, Alessio, Zicovich-Wilson, Claudio M, Sanz, Javier Fdez
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 11.01.2011
• Subjects: Quantum Electronic Structure
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct100430q

The outstanding catalytic properties of cerium oxides rely on the easy Ce3+ ↔ Ce4+ redox conversion, which however constitutes a challenge in density functional based theoretical chemistry due to the strongly correlated nature of the 4f electrons present in the reduced materials. In this work, we report an analysis of the performance of five exchange-correlation functionals (HH, HHLYP, PBE0, B3LYP, and B1-WC) implemented in the CRYSTAL06 code to describe three properties of ceria: crystal structure, band gaps, and reaction energies of the CeO2 → Ce2O3 process. All five functionals give values for cell parameters that are in fairly good agreement with experiment, although the PBE0 hybrid functional is found to be the most accurate. Band gaps, 2p-4f-5d in the case of CeO2 and 4f-5d in the case of Ce2O3, are found to be, in general, overestimated and drop off when the amount of Hartree−Fock exchange in the exchange-correlation functional decreases. In contrast, the reaction energies are found to be underestimated, and increase when the amount of HF exchange lowers. Overall, at its standard formulation, the B1-WC functional seems to be the best choice as it provides good band gaps and reaction energies, and very reasonable crystal parameters.