title: Predicting Pt-195 NMR chemical shift using new relativistic all-electron basis set.
abstract: Predicting NMR properties is a valuable tool to assist the experimentalists in the characterization of molecular structure. For heavy metals, such as Pt-195, only a few computational protocols are available. In the present contribution, all-electron Gaussian basis sets, suitable to calculate the Pt-195 NMR chemical shift, are presented for Pt and all elements commonly found as Pt-ligands. The new basis sets identified as NMR-DKH were partially contracted as a triple-zeta doubly polarized scheme with all coefficients obtained from a Douglas-Kroll-Hess (DKH) second-order scalar relativistic calculation. The Pt-195 chemical shift was predicted through empirical models fitted to reproduce experimental data for a set of 183 Pt(II) complexes which NMR sign ranges from -1000 to -6000 ppm. Furthermore, the models were validated using a new set of 75 Pt(II) complexes, not included in the descriptive set. The models were constructed using non-relativistic Hamiltonian at density functional theory (DFT-PBEPBE) level with NMR-DKH basis set for all atoms. For the best model, the mean absolute deviation (MAD) and the mean relative deviation (MRD) were 150 ppm and 6%, respectively, for the validation set (75 Pt-complexes) and 168 ppm (MAD) and 5% (MRD) for all 258 Pt(II) complexes. These results were comparable with relativistic DFT calculation, 200 ppm (MAD) and 6% (MRD). © 2016 Wiley Periodicals, Inc.
authors: NEQC: Núcleo de Estudos em Química Computacional, Departamento de Química - ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36.036-900, Juiz de Fora, MG, Brasil. diegofspaschoal@gmail.com, diegofspaschoal@macae.ufrj.br.|NQTCM: Núcleo de Química Teórica e Computacional de Macaé, Polo Ajuda, Universidade Federal do Rio de Janeiro, Campus UFRJ-Macaé, 27.971-525, Macaé, RJ, Brasil. diegofspaschoal@gmail.com, diegofspaschoal@macae.ufrj.br.
authors: D
authors: D
authors: Paschoal
authors: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, Amsterdam, HV, 1081, the Netherlands.
authors: C Fonseca
authors: CF
authors: Guerra
authors: GQAQ: Grupo de Química Analítica e Quimiometria, Departamento de Química - ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36.036-900, Juiz de Fora, MG, Brasil.
authors: M A L
authors: MA
authors: de Oliveira
authors: GQC: Grupo de Química Computacional, Departamento de Química, Universidade Federal de Lavras, 37.200-000, Lavras, MG, Brasil.
authors: T C
authors: TC
authors: Ramalho
authors: NEQC: Núcleo de Estudos em Química Computacional, Departamento de Química - ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36.036-900, Juiz de Fora, MG, Brasil. diegofspaschoal@macae.ufrj.br.
authors: H F
authors: HF
authors: Dos Santos
keywords: NMR; NMR-DKH; Pt-195 chemical shift; ab initio; all-electron Gaussian basis set; platinum complexes; relativistic effects; structure prediction