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

Abstract

In our report, 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 suggested 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:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1574447
Alternate Identifier(s):
OSTI ID: 1570052
Report Number(s):
SAND-2019-12496J
Journal ID: ISSN 1463-9076; PPCPFQ; 680399; TRN: US2100017
Grant/Contract Number:  
AC04-94AL85000; SC0012577; NA0003525; UNCAGE-ME Energy Frontier Research Center (EFRC) A; #DE-SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 21; Journal Issue: 41; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vogel, Dayton J., Sava Gallis, Dorina F., Nenoff, Tina M., and Rimsza, Jessica M. Structure and electronic properties of rare earth DOBDC metal–organic-frameworks. United States: N. p., 2019. Web. doi:10.1039/C9CP04038B.
Vogel, Dayton J., Sava Gallis, Dorina F., Nenoff, Tina M., & Rimsza, Jessica M. Structure and electronic properties of rare earth DOBDC metal–organic-frameworks. United States. https://doi.org/10.1039/C9CP04038B
Vogel, Dayton J., Sava Gallis, Dorina F., Nenoff, Tina M., and Rimsza, Jessica M. Fri . "Structure and electronic properties of rare earth DOBDC metal–organic-frameworks". United States. https://doi.org/10.1039/C9CP04038B. https://www.osti.gov/servlets/purl/1574447.
@article{osti_1574447,
title = {Structure and electronic properties of rare earth DOBDC metal–organic-frameworks},
author = {Vogel, Dayton J. and Sava Gallis, Dorina F. and Nenoff, Tina M. and Rimsza, Jessica M.},
abstractNote = {In our report, we apply density functional theory (DFT) to investigate rare-earth metal organic frameworks (RE-MOFs), RE12(μ3-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 suggested 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.},
doi = {10.1039/C9CP04038B},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 41,
volume = 21,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Periodic 3D structure of activated Eu-DOBDC with a single unit cell centrally located and highlighted by a blue box. Colors: Eu(green), 0(red), C(brown), and H(white)

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