Origin of the strong interaction between polar molecules and copper(II) paddle-wheels in metal organic frameworks

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dc.contributor.authorOngari, Daniele
dc.contributor.authorTiana, Davide
dc.contributor.authorStoneburner, Samuel J.
dc.contributor.authorGagliardi, Laura
dc.contributor.authorSmit, Berend
dc.contributor.funderNational Center of Competence in Research Materials’ Revolution: Computational Design and Discovery of Novel Materialsen
dc.contributor.funderSchweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschungen
dc.contributor.funderH2020 European Research Councilen
dc.contributor.funderU.S. Department of Energyen
dc.date.accessioned2018-07-06T14:40:26Z
dc.date.available2018-07-06T14:40:26Z
dc.date.issued2017-06-27
dc.date.updated2018-07-03T11:03:02Z
dc.description.abstractThe 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.en
dc.description.sponsorshipCentro Svizzero di Calcolo Scientifico, CSCS (Swiss National Supercomputing Center (CSCS) under Project no. s611); U.S. Department of Energy ( Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0012702)en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationOngari, D., Tiana, D., Stoneburner, S. J., Gagliardi, L. and Smit, B. (2017) 'Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks', The Journal of Physical Chemistry C, 121(28), pp. 15135-15144.en
dc.identifier.doi10.1021/acs.jpcc.7b02302
dc.identifier.endpage15144en
dc.identifier.issn1932-7447
dc.identifier.issued28en
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.identifier.startpage15135en
dc.identifier.urihttps://hdl.handle.net/10468/6429
dc.identifier.volume121en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::ERC::ERC-ADG/666983/EU/The Materials Genome in Action/MaGicen
dc.relation.urihttp://dx.doi.org/10.1021/acs.jpcc.7b02302
dc.rights© 2017 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposesen
dc.rights.urihttps://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen
dc.subjectCarbon dioxide adsorptionen
dc.subjectDensity functional theory methodsen
dc.subjectInteraction energiesen
dc.subjectMetal organic frameworken
dc.subjectMultireference wave functionsen
dc.subjectParametrizationsen
dc.subjectPerturbation theoryen
dc.subjectStrong interactionen
dc.subjectCarbonen
dc.subjectCarbon dioxideen
dc.subjectCopperen
dc.subjectDensity functional theoryen
dc.subjectGas adsorptionen
dc.subjectMoleculesen
dc.subjectOrganometallicsen
dc.subjectPerturbation techniquesen
dc.subjectPropellersen
dc.titleOrigin of the strong interaction between polar molecules and copper(II) paddle-wheels in metal organic frameworksen
dc.typeArticle (peer-reviewed)en
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