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

Molecules

Marjan Krstić¹  Dmitry I. Sharapa²  Karin Fink³ 

[1] Institute for Theoretical Solid State Physics (TFP), Karlsruhe Institute of Technology (KIT), Wolfgang-Gaede-Str. 1, 76131 Karlsruhe, Germany;Institute of Catalysis Research and Technology (IKFT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany;Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany;

关键词: copper paddle-wheel;    HKUST-1;    MOF;    educts adsorption;    binding energies;    DFT;   

DOI  :  10.3390/molecules27030912

来源: DOAJ

【 摘 要 】

We report a theoretical study of the adsorption of a set of small molecules (C₂H₂, CO, CO₂, O₂, H₂O, CH₃OH, C₂H₅OH) 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 (MP2, SOS–MP2, MP3, 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.

【 授权许可】

Unknown