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

Daniele Ongari, Davide Tiana, Samuel J. Stoneburner, Laura Gagliardi, Berend Smit

Research output: Contribution to journalArticle

9 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)15135-15144
Number of pages10
JournalJournal of Physical Chemistry C
Volume121
Issue number28
DOIs
StatePublished - Jul 20 2017

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paddles
wheels
Copper
Wheels
formic acid
Metals
copper
Molecules
metals
molecules
formates
adsorption
interactions
Wave functions
Adsorption isotherms
Carbon Dioxide
field theory (physics)
Density functional theory
Cations
carbon dioxide

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Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. / Ongari, Daniele; Tiana, Davide; Stoneburner, Samuel J.; Gagliardi, Laura; Smit, Berend.

In: Journal of Physical Chemistry C, Vol. 121, No. 28, 20.07.2017, p. 15135-15144.

Research output: Contribution to journalArticle

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. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 28. pp. 15135-15144.
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