| Texto completo | |
| Autor(es): |
Schenberg, Leonardo Araujo
;
Ducati, Lucas Colucci
;
Autschbach, Jochen
Número total de Autores: 3
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Inorganic Chemistry; v. 63, n. 4, p. 8-pg., 2024-01-11. |
| Resumo | |
Ab initio molecular dynamics (AIMD) sampling followed by relativistic density functional theory (DFT) Hg-199 NMR calculations were performed for Hg organometallic complexes in water, dimethyl sulfoxide, and chloroform. The spin-orbit coupling, a relativistic effect, is a key factor for predicting delta(Hg) and (1)J(Hg-C) accurately, in conjunction with a dynamic treatment of the systems. Good agreement between the theoretical and experimental results is reached by adopting implicit (based on a continuum model) and explicit (solvent molecules treated quantum mechanically) solvation models. Broader trends appearing in the experimental data available in the literature are reproduced by the calculations, and therefore, quantum chemistry is able to assist in the assignment and interpretation of Hg-199 NMR data. Less pronounced trends, such as changes in the Hg-199 chemical shift in different systems with the same atom types bound to Hg, are too weak to be predicted reliably by the current state-of-the-art theoretical methods based on AIMD sampling and relativistic DFT with hybrid functionals for NMR calculations. (AU) | |
| Processo FAPESP: | 17/17750-3 - Efeito do Solvente em Parâmetros Espectroscópicos de RMN por Dinâmica Molecular ab initio |
| Beneficiário: | Lucas Colucci Ducati |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |
| Processo FAPESP: | 19/18727-0 - Estudo de compostos organometálicos de 199Hg em solução por dinâmica molecular ab initio e cálculos relativísticos de RMN |
| Beneficiário: | Leonardo Araujo Schenberg |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |
| Processo FAPESP: | 22/10688-9 - Estudo do efeito de solvatação do clorofórmio em propriedades de RMN de 199Hg de derivados de metilmercúrio por dinâmica molecular ab initio e cálculos relativísticos |
| Beneficiário: | Leonardo Araujo Schenberg |
| Modalidade de apoio: | Bolsas no Exterior - Estágio de Pesquisa - Doutorado Direto |