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Chemical reactivity studies by the natural orbital functional second-order Møller–Plesset (NOF-MP2) method: water dehydrogenation by the scandium cation

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Abstract

The reliability of the recently proposed natural orbital functional supplemented with second-order Møller–Plesset calculations (NOF-MP2) has been assessed for the mechanistic studies of elementary reactions of transition metal compounds by investigating the dehydrogenation of water by the scandium cation. Both high- and low-spin state potential energy surfaces have been searched thoroughly. Special attention has been paid to the assessment of the capability of the NOF-MP2 method to describe the strong, both static and dynamic, electron correlation effects on the reactivity of Sc\(^{+}\)(\(^{3}\)D, \(^{1}\)D) with water. In agreement with experimental observations, our calculations correctly predict that the only exothermic products are the lowest-lying ScO\(^{+} (^{1}{\Sigma })\) and H\(_{2}(^{1}{\Sigma }_{g}^{+})\) species. Nevertheless, an in-depth analysis of the reaction paths leading to several additional products was carried out, including the characterization of various minima and several key transition states. Our results have been compared with the highly accurate multiconfigurational supplemented with quasi-degenerated perturbation theory, MCQDPT, wavefunction-type calculations, and the available experimental data. It is observed that NOF-MP2 is able to give a satisfactorily quantitative agreement, with a performance on par with that of the MCQDPT method.

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Acknowledgements

The authors thank for technical and human support provided by IZO-SGI SGIker of UPV/EHU and European funding (ERDF and ESF) and DIPC for the generous allocation of computational resources. Financial support comes from the Spanish Office for Scientific Research (MCIU /AEI /FEDER, UE), Ref. PGC2018-097529-B-100, and Eusko Jaurlaritza (Basque Government), Ref. IT1254-19.

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  1. Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia International Physics Center (DIPC), P. K. 1072, 20080, Donostia, Euskadi, Spain

    Jose M. Mercero, Jesus M. Ugalde & Mario Piris

  2. IKERBASQUE, Basque Foundation for Science, 48009, Bilbao, Euskadi, Spain

    Mario Piris

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  1. Jose M. Mercero
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  2. Jesus M. Ugalde
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Correspondence to Mario Piris.

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Published as part of the special collection of articles “Festschrift in honour of Prof. Ramon Carbó-Dorca”.

Financial support comes from MCIU/AEI/FEDER, UE (PGC2018-097529-B-100) and Eusko Jaurlaritza (Ref. IT1254-19).

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Mercero, J.M., Ugalde, J.M. & Piris, M. Chemical reactivity studies by the natural orbital functional second-order Møller–Plesset (NOF-MP2) method: water dehydrogenation by the scandium cation. Theor Chem Acc 140, 74 (2021). https://doi.org/10.1007/s00214-021-02775-4

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