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Author Mann, Gregory W. ♦ Lee, Kyuho ♦ Cococcioni, Matteo ♦ Smit, Berend ♦ Neaton, Jeffrey B.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ BINDING ENERGY ♦ CARBON DIOXIDE ♦ COMPUTERIZED SIMULATION ♦ DENSITY FUNCTIONAL METHOD ♦ EXPERIMENTAL DATA ♦ LATTICE PARAMETERS ♦ MOLECULES ♦ ORGANOMETALLIC COMPOUNDS ♦ TRANSITION ELEMENTS ♦ U VALUES ♦ VAN DER WAALS FORCES
Abstract We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2016-05-07
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 144
Issue Number 17


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