Chemical reactivity studies by the natural orbital functional second-order Møller–Plesset (NOF-MP2) method: water dehydrogenation by the scandium cation
| العنوان: | 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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| المؤلفون: | Mario Piris, Jose M. Mercero, Jesus M. Ugalde |
| المصدر: | Theoretical Chemistry Accounts. 140 |
| بيانات النشر: | Springer Science and Business Media LLC, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Physics, 010304 chemical physics, Electronic correlation, Møller–Plesset perturbation theory, chemistry.chemical_element, Order (ring theory), Thermodynamics, 010402 general chemistry, 01 natural sciences, Potential energy, Transition state, 0104 chemical sciences, chemistry, 0103 physical sciences, Elementary reaction, Scandium, Physical and Theoretical Chemistry, Perturbation theory |
| الوصف: | 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. |
| تدمد: | 1432-2234 1432-881X |
| DOI: | 10.1007/s00214-021-02775-4 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::ae565637056321942db10851701f7bb5 https://doi.org/10.1007/s00214-021-02775-4 |
| Rights: | CLOSED |
| رقم الانضمام: | edsair.doi...........ae565637056321942db10851701f7bb5 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 14322234 1432881X |
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| DOI: | 10.1007/s00214-021-02775-4 |