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Title: Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion, Valais, Switzerland
  2. Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States); Federal Inst. of Technology (EPFL), Lausanne (Switzerland); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Swiss National Science Foundation (SNSF); European Research Council (ERC)
OSTI Identifier:
1369080
Alternate Identifier(s):
OSTI ID: 1372320
Grant/Contract Number:  
SC0012702; 666983
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. C Journal Volume: 121 Journal Issue: 28; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02302.
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, & Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States. doi:10.1021/acs.jpcc.7b02302.
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. Fri . "Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks". United States. doi:10.1021/acs.jpcc.7b02302.
@article{osti_1369080,
title = {Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks},
author = {Ongari, Daniele and Tiana, Davide and Stoneburner, Samuel J. and Gagliardi, Laura and Smit, Berend},
abstractNote = {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.},
doi = {10.1021/acs.jpcc.7b02302},
journal = {Journal of Physical Chemistry. C},
number = 28,
volume = 121,
place = {United States},
year = {2017},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.jpcc.7b02302

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Cited by: 2 works
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