| Texto completo | |
| Autor(es): |
Batista, Patrick R.
;
Ducati, Lucas C.
;
Autschbach, Jochen
Número total de Autores: 3
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Journal of Chemical Physics; v. 160, n. 11, p. 12-pg., 2024-03-21. |
| Resumo | |
Treating Pt-195 nuclear magnetic resonance parameters in solution remains a considerable challenge from a quantum chemistry point of view, requiring a high level of theory that simultaneously takes into account the relativistic effects, the dynamic treatment of the solvent-solute system, and the dynamic electron correlation. A combination of Car-Parrinello molecular dynamics (CPMD) and relativistic calculations based on two-component zeroth order regular approximation spin-orbit Kohn-Sham (2c-ZKS) and four-component Dirac-Kohn-Sham (4c-DKS) Hamiltonians is performed to address the solvent effect (water) on the conformational changes and (1)J(PtPt) coupling. A series of bridged PtIII dinuclear complexes [L-1-Pt-2(NH3)(4)(Am)(2)-L-2](n+) (Am = alpha-pyrrolidonate and pivalamidate; L = H2O, Cl-, and Br-) are studied. The computed Pt-Pt coupling is strongly dependent on the conformational dynamics of the complexes, which, in turn, is correlated with the trans influence among axial ligands and with the angle N-C-O from the bridging ligands. The J-coupling is decomposed in terms of dynamic contributions. The decomposition reveals that the vibrational and explicit solvation contributions reduce (1)J(PtPt) of diaquo complexes (L-1 = L-2 = H2O) in comparison to the static gas-phase magnitude, whereas the implicit solvation and bulk contributions correspond to an increase in (1)J(PtPt) in dihalo (L-1 = L-2 = X-) and aquahalo (L-1 = H2O; L-2 = X-) complexes. Relativistic treatment combined with CPMD shows that the 2c-ZKS Hamiltonian performs as well as 4c-DKS for the (1)J(PtPt) coupling. (AU) | |
| Processo FAPESP: | 18/07308-4 - Efeito do solvente em cálculos de tensor blindagem e constante de acoplamento de complexos dinucleares de platina (III) via dinâmica molecular ab initio |
| Beneficiário: | Patrick Rodrigues Batista |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado |
| 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 |