Actions for Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks [electronic resource].

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Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2017.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 15,135-15,144 : digital, PDF file
Additional Creators
United States. Department of Energy. Office of Basic Energy Sciences, National Science Foundation (U.S.), Belgium. Office of the European Research Council Executive Agency (ERCEA), and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.
Report Numbers
E 1.99:1372320
Subject(s)
Note
Published through SciTech Connect.
06/27/2017.
Journal of Physical Chemistry. C 121 28 ISSN 1932-7447 AM
Daniele Ongari; Davide Tiana; Samuel J. Stoneburner; Laura Gagliardi; Berend Smit.
Univ. of Minnesota, Minneapolis, MN (United States)
Federal Inst. of Technology (EPFL), Lausanne (Switzerland)
Funding Information
SC0012702
666983
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