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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–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, 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 CO 2 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. Federal Inst. of Technology (EPFL), Lausanne (Switzerland). Inst. of Chemical Sciences and Engineering. Lab. of Molecular Simulation
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Minnesota Supercomputing Inst.
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) (SC-22); 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:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
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. Tue . "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 = {Tue Jun 27 00:00:00 EDT 2017},
month = {Tue Jun 27 00:00:00 EDT 2017}
}

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

Citation Metrics:
Cited by: 1 work
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