caa a22 4500 605512604 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2642-0 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2642-0 Metal coordination study at Ag and Cd sites in crown thioether complexes through DFT calculations and hyperfine parameters [Elektronische Daten] [Rafael do Nascimento, Filipe Lima, Marcos Gonçalves, Leonardo Errico, Mario Rentería, Helena Petrilli] 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. Springer-Verlag Berlin Heidelberg, 2015 Crown thioether metal complexes nationallicence Hyperfine interactions nationallicence Electric field gradient nationallicence Perturbed angular correlations nationallicence Density functional calculations nationallicence Silver nationallicence Cadmium nationallicence do Nascimento Rafael Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut Lima Filipe Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut Gonçalves Marcos Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut Errico Leonardo Departamento de Física, Instituto de Física La Plata (IFLP, CCT-La Plata, CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 67, 1900, La Plata, Argentina aut Rentería Mario Departamento de Física, Instituto de Física La Plata (IFLP, CCT-La Plata, CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 67, 1900, La Plata, Argentina aut Petrilli Helena Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-7 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2642-0 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2642-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- do Nascimento Rafael Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut NATIONALLICENCE 700 1- Lima Filipe Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut NATIONALLICENCE 700 1- Gonçalves Marcos Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut NATIONALLICENCE 700 1- Errico Leonardo Departamento de Física, Instituto de Física La Plata (IFLP, CCT-La Plata, CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 67, 1900, La Plata, Argentina aut NATIONALLICENCE 700 1- Rentería Mario Departamento de Física, Instituto de Física La Plata (IFLP, CCT-La Plata, CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 67, 1900, La Plata, Argentina aut NATIONALLICENCE 700 1- Petrilli Helena Instituto de Física, Universidade de São Paulo, Rua do Matão Travessa R, Nr.187, Cidade Universitária, CP 66318, 05508-090, São Paulo, Brazil aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-7 1610-2940 21:4<1 2015 21 894