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

ABSTRACT: 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.

SUBMITTER: Krstic M

PROVIDER: S-EPMC8840508 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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

Krstić Marjan M Fink Karin K Sharapa Dmitry I DI

Molecules (Basel, Switzerland) 20220128 3

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 ...[more]

PMID: 35164179

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Project description:The experimental electron-density distribution in two isostructural complexes, tetrakis(μ2-acetato)diaquadicopper(II) [H2OCu(ac)2Cu(ac)2H2O] and tetrakis(μ2-acetato)diaquadichromium(II) [H2OCr(ac)2Cr(ac)2H2O], has been studied and compared. The experimental electron density distribution in two isostructural and isomorphous complexes, tetrakis(μ2-acetato)diaquadicopper(II) [H2OCu(ac)2Cu(ac)2H2O] (I) and tetrakis(μ2-acetato)diaquadichromium(II), [H2OCr(ac)2Cr(ac)2H2O] (II), has been obtained from high-resolution X-ray diffraction data in order to shed light on the bonding properties in the compounds studied. It has been shown that from accurate X-ray data it is possible to discuss the bonding capability of the metal atom (Cu/Cr) and the ligands in these complexes. A comparison of results obtained from averaged and non-averaged X-ray data demonstrates that using the non-averaged data and introducing an anisotropic correction for secondary extinction errors provides a more detailed distribution of the electron density in the area of the metal atoms. In both complexes studied, the bonding of the acetate oxygen atom to the central metal atom is significantly affected by the formation of hydrogen bonds. The electron density and its Laplacian at the bond critical point of metal–oxygen coordination bonds for those oxygen atoms not involved in the intermolecular hydrogen bonds are approximately 10% larger compared with the case when oxygen atoms take part in hydrogen bonds with the neighboring water molecules. It is shown that metal–oxygen bonds in a quasi-equatorial plane are typical coordination bonds and differ significantly from the apical metal–oxygen bond. Metal–metal interaction with a small positive value of the electron density Laplacian at this bond critical point is mainly of electrostatic character. The metal–metal interaction is definitely not a bond according to the classical definition. Based on a search of the Cambridge Structural Database, it can be argued that there are four typical coordination bonds in the [CuO6] chromophore, similar to the four Cu—O coordination bonds in the basal plane of the CuO5 pyramid in one of the complexes under study.

Dataset Information

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

Publications

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

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