How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?
| Autor: | Régis T. Santiago, Roberto L. A. Haiduke, Renato Pereira Orenha, Sérgio E. Galembeck |
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| Rok vydání: | 2017 |
| Předmět: |
REAÇÕES QUÍMICAS
010304 chemical physics Series (mathematics) Trans effect Scalar (mathematics) chemistry.chemical_element Thermodynamics General Chemistry 010402 general chemistry 01 natural sciences Chemical reaction 0104 chemical sciences Ruthenium Computational Mathematics chemistry 0103 physical sciences Atomic physics Relativistic quantum chemistry Isomerization Basis set |
| Zdroj: | Repositório Institucional da USP (Biblioteca Digital da Produção Intelectual) Universidade de São Paulo (USP) instacron:USP |
| ISSN: | 0192-8651 |
| DOI: | 10.1002/jcc.24762 |
| Popis: | Two treatments of relativistic effects, namely effective core potentials (ECP) and all-electron scalar relativistic effects (DKH2), are used to obtain geometries and chemical reaction energies for a series of ruthenium complexes in B3LYP/def2-TZVP calculations. Specifically, the reaction energies of reduction (A-F), isomerization (G-I), and Cl- negative trans influence in relation to NH3 (J-L) are considered. The ECP and DKH2 approaches provided geometric parameters close to experimental data and the same ordering for energy changes of reactions A-L. From geometries optimized with ECP, the electronic energies are also determined by means of the same ECP and basis set combined with the computational methods: MP2, M06, BP86, and its derivatives, so as B2PLYP, LC-wPBE, and CCSD(T) (reference method). For reactions A-I, B2PLYP provides the best agreement with CCSD(T) results. Additionally, B3LYP gave the smallest error for the energies of reactions J-L. © 2017 Wiley Periodicals, Inc. |
| Databáze: | OpenAIRE |
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