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Structure and electronic properties of rare earth DOBDC metal–organic-frameworks

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Abstract

Here, we apply density functional theory (DFT) to investigate rare-earth metal organic frameworks (RE-MOFs), RE123-OH)16(C8O6H4)8(C8O6H5)4 (RE = Y, Eu, Tb, Yb), and characterize the level of theory needed to accurately predict structural and electronic properties in MOF materials with 4f-electrons. A two-step calculation approach of geometry optimization with spin-restricted DFT and large core potential (LCPs), and detailed electronic structures with spin-unrestricted DFT with a full valence potential + Hubbard U correction is investigated. Spin-restricted DFT with LCPs resulted in good agreement between experimental lattice parameters and optimized geometries, while a full valence potential is necessary for accurate representation of the electronic structure. The electronic structure of Eu-DOBDC MOF indicated a strong dependence on the treatment of highly localized 4f-electrons and spin polarization, as well as variation within a range of Hubbard corrections (U = 1–9 eV). For Hubbard corrected spin-unrestricted calculations, a U value of 1–4 eV maintains the non-metallic character of the band gap with slight deviations in f-orbital energetics. When compared with experimentally reported results, the importance of the full valence calculation and the Hubbard correction in correctly predicting the electronic structure is highlighted.

Graphical abstract: Structure and electronic properties of rare earth DOBDC metal–organic-frameworks

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Publication details

The article was received on 18 Jul 2019, accepted on 03 Oct 2019 and first published on 11 Oct 2019


Article type: Paper
DOI: 10.1039/C9CP04038B
Phys. Chem. Chem. Phys., 2019, Advance Article

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    Structure and electronic properties of rare earth DOBDC metal–organic-frameworks

    D. J. Vogel, D. F. Sava Gallis, T. M. Nenoff and J. M. Rimsza, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C9CP04038B

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