Performance of van der Waals Corrected Functionals for Guest Adsorption in the M2(dobdc) Metal-Organic Frameworks

Published

April 24, 2017

Author(s)

Bess Vlaisavljevich, Johanna Huck, Zeric Hulvey, Kyuho Lee, Jarad A. Mason, Jeffrey B. Neaton, Jeffrey R. Long, Craig Brown, Dario Alfe, Angelos Michaelides, Berend Smit

Abstract

Small molecule binding in metal-organic frameworks (MOFs) can be accurately studied both experimentally and computationally, provided the proper tools are employed. Herein, we compare and contrast properties associated with guest binding with density functional theory (DFT) calculations using eight different functionals for the M₂(dobdc) (dobdc^4- = 2,5-dioxido,1,4-benzenedicarboxylate) series where M = Mg, Mn, Fe, Co, Ni, Cu, and Zn. Additonally, we perform Quantum Monte Carlo (QMC) calculations for one system to determine if this method can be used to assess the performance of DFT. We also make comparisons with previously published experimental results for carbon dioxide and water, and present new methane neutron powder diffraction (NPD) data for further comparison. All of the functionals are able to predict the experimental variation in the binding energy from one metal to the next; however, how we interpret the performance of the functionals depends on which value we compare against. If we compare against experimental values, we would conclude that the optB86b-vdW and optB88-vdW functionals systematically overestimate the binding strenght, while the vdW-DF2 functionals corrects for this providing a good description of binding energies. On the other hand, if the QMC calculation is used as the "gold-standard" then all of the functionals yield results within the error of the higher-level calculation. However, we note that the newest of the functionals, rev-vdW-DF2 should be used in place of vdW-DF2 should be used in place of vdW-DF2 as it yields both good bond distance and binding energies. Likewise the M06-L functional performed quite well.

Citation

Journal of Physical Chemistry A

Volume

121

Issue

21

Pub Type

Journals

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Keywords

density-functional theory, metal-organic framework, van der waals

Citation

Vlaisavljevich, B. , Huck, J. , Hulvey, Z. , Lee, K. , Mason, J. , Neaton, J. , Long, J. , Brown, C. , Alfe, D. , Michaelides, A. and Smit, B. (2017), Performance of van der Waals Corrected Functionals for Guest Adsorption in the M₂(dobdc) Metal-Organic Frameworks, Journal of Physical Chemistry A, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=922625 (Accessed October 24, 2025)