Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 21, Issue 41, Pages 23085-23093Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9cp04038b
Keywords
-
Funding
- UNCAGE-ME, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012577]
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA0003525]
Ask authors/readers for more resources
Here, we apply density functional theory (DFT) to investigate rare-earth metal organic frameworks (RE-MOFs), RE12(mu(3)-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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available