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

Autor: Mario Piris, Jose M. Mercero, Jesus M. Ugalde
Rok vydání: 2021
Předmět:
Zdroj: Theoretical Chemistry Accounts. 140
ISSN: 1432-2234
1432-881X
DOI: 10.1007/s00214-021-02775-4
Popis: The reliability of the recently proposed natural orbital functional supplemented with second-order Moller–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.
Databáze: OpenAIRE
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