First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

Gregory W Mann; Kyuho Lee; Matteo Cococcioni; Berend Smit; Jeffrey B Neaton

doi:10.1063/1.4947240

First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

J Chem Phys. 2016 May 7;144(17):174104. doi: 10.1063/1.4947240.

Authors

Gregory W Mann¹, Kyuho Lee², Matteo Cococcioni³, Berend Smit¹, Jeffrey B Neaton⁴

Affiliations

¹ Department of Chemistry, University of California, Berkeley, California 94720, USA.
² Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA.
³ Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland.
⁴ Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

PMID: 27155622
DOI: 10.1063/1.4947240

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 CO2-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 CO2 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.