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The Adsorption of Small Molecules on the Copper Paddle-Wheel: Influence of the Multi-Reference Ground State

Krstić, Marjan; Fink, Karin ORCID iD icon; Sharapa, Dmitry I. ORCID iD icon

Abstract:

We report a theoretical study of the adsorption of a set of small molecules (C$_{2}$H$_{2}$, CO, CO$_{2}$, O$_{2}$, H$_{2}$O, CH$_{3}$OH, C$_{2}$H$_{5}$OH) on the metal centers of the “copper paddle-wheel”—a key structural motif of many MOFs. A systematic comparison between DFT of different rungs, single-reference post-HF methods (MP$_{2}$, SOS–MP$_{2}$, MP$_{3}$, DLPNO–CCSD(T)), and multi-reference approaches (CASSCF, DCD–CAS(2), NEVPT2) is performed in order to find a methodology that correctly describes the complicated electronic structure of paddle-wheel structure together with a reasonable description of non-covalent interactions. Apart from comparison with literature data (experimental values wherever possible), benchmark calculations with DLPNO–MR–CCSD were also performed. Despite tested methods show qualitative agreement in the majority of cases, we showed and discussed reasons for quantitative differences as well as more fundamental problems of specific cases


Verlagsausgabe §
DOI: 10.5445/IR/1000142844
Veröffentlicht am 09.02.2022
Originalveröffentlichung
DOI: 10.3390/molecules27030912
Scopus
Zitationen: 2
Web of Science
Zitationen: 2
Dimensions
Zitationen: 2
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Katalyseforschung und -technologie (IKFT)
Institut für Nanotechnologie (INT)
Institut für Theoretische Festkörperphysik (TFP)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2022
Sprache Englisch
Identifikator ISSN: 1420-3049
KITopen-ID: 1000142844
HGF-Programm 43.32.01 (POF IV, LK 01) Molecular Materials Basis for Optics & Photonics
Erschienen in Molecules
Verlag MDPI
Band 27
Heft 3
Seiten Art.-Nr.: 912
Schlagwörter copper paddle-wheel; HKUST-1; MOF; educts adsorption; binding energies; DFT; single-reference methods; multi-reference system
Nachgewiesen in Dimensions
Scopus
Web of Science
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