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 journalArticlepeer-review

26 Scopus citations

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

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

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