Metal coordination study at Ag and Cd sites in Crown Thioether complexes through DFT calculations and hyperfine parameters

Structural and electronic properties of [C12H24S6X], [C13H26S6OX], and [C14H28S6OX] (X: Ag+ , Cd2+) crown thioether complexes were investigated within the framework of the density functional theory (DFT) using the projector augmented wave (PAW) method. The theoretical results were compared with time...

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Detalles Bibliográficos
Autores: Nascimento, Rafael R. do, Lima, Filipe C. D. A., Gonçalves, Marcos B., Errico, Leonardo Antonio, Rentería, Mario, Petrilli, Helena M.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/47929
Acceso en línea:http://hdl.handle.net/11336/47929
Access Level:acceso abierto
Palabra clave:Crown Thioether Metal Complexes
Hyperfine Interactions
Electric Field Gradient
Perturbed Angular Correlations
Density Functional Calculations
Silver
Cadmium
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
Descripción
Sumario:Structural and electronic properties of [C12H24S6X], [C13H26S6OX], and [C14H28S6OX] (X: Ag+ , Cd2+) crown thioether complexes were investigated within the framework of the density functional theory (DFT) using the projector augmented wave (PAW) method. The theoretical results were compared with time-differential perturbed γ?γ angular correlations (TDPAC) experiments reported in the literature using the 111Ag→111Cd probe. In the case of X=Ag+ , a refinement of the structure was performed and the predicted equilibrium structures compared with available X-ray diffraction experimental data. Structural distortions induced by replacing Ag+ with Cd2+ were investigated as well as the electric-field gradient (EFG) tensor at the Cd2+ sites. Our results suggest that the EFG at Cd2+ sites corresponds to the Ag+ coordination sphere structure, i.e., before the structural relaxations of the molecule with X=Cd2+ are completed. The results are discussed in terms of the characteristics of the TDPAC 111Ag→111Cd probe and the time window of the measurement, and provide an interesting tool with which to probe molecular relaxations.