First principles study of rare-earth oxides

Abstract

The self-interaction-corrected local-spin-density approximation is used to describe the electronic structure of dioxides, REO${}_2$, and sesquioxides, RE${}_2$O${}_3$, for the rare earths, RE=Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy and Ho. The valencies of the rare earth ions are determined from total energy minimization. We find Ce, Pr, Tb in their dioxides to have the tetravalent configuration, while for all the sesquioxides the trivalent groundstate configuration is found to be the most favourable. The calculated lattice constants for these valency configurations are in good agreement with experiment. Total energy considerations are exploited to show the link between oxidation and $f$-electron delocalization, and explain why, among the dioxides, only the CeO${}_2$, PrO${}_2$, and TbO${}_2$ exist in nature. Tetravalent NdO${}_2$ is predicted to exist as a metastable phase - unstable towards the formation of hexagonal Nd${}_2$O${}_3$.

22 pages, 4 tables, 7 figures

References in corpus (2)

• Localized 4f States and Dynamic Jahn-Teller Effect in PrO2
• Cooperative Jahn-Teller Distortion in PrO2

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• Role of intermediate 4$f$ states in tuning the band structure of high entropy oxides
• A DFT+U study on the contribution of 4f electrons to oxygen vacancy formation and migration in Ln-doped CeO2
• High multipole transitions in NIXS: valence and hybridization in 4f systems
• Anisotropic Exchange Interaction between Non-magnetic Europium Cations in Eu_2O_3
• Electronic structure and energy level schemes of RE3+:LaSi3N5 and RE2+:LaSi3N5-xOx phosphors (RE= Ce, Pr, Nd, Pm, Sm, Eu) from first principles
• Lanthanide impurities in wide bandgap semiconductors: a possible roadmap for spintronic devices
• Combining semi-local exchange with dynamical mean-field theory: electronic structure and optical response of rare-earth sesquioxides