Theoretical Isotropic Hyperfine Coupling Constants of Third-Row Nuclei (29Si, 31P, and 33S)
- 30 July 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 109 (33) , 7626-7635
- https://doi.org/10.1021/jp0522361
Abstract
In a previous paper (Hermosilla, L.; Calle, P.; Garcia de la Vega, J. M.; Sieiro, C. J. Phys. Chem. A 2005, 109, 1114), an adequate computational protocol for the calculation of isotropic hyperfine coupling constants (hfcc's) was proposed. The main conclusion concerns the reliability of the scheme B3LYP/TZVP//B3LYP/6-31G* in the predictions of hfcc's with low computational cost. In the present study, we gain insight into the behavior of the above functional/basis set scheme on nuclei of the third row, for which few systematic studies have been carried out up to the present date. The systems studied are neutral, cationic, anionic, localized, and conjugated radicals, containing (29)Si, (31)P, and (33)S nuclei. After carrying out a regression analysis, we conclude that density functional theory (DFT) predictions on the hfcc's of the third-row nuclei are reliable for B3LYP/TZVP by using an optimized geometry with B3LYP/6-31G* combination. By comparison with other much more computationally demanding schemes, namely, B3LYP/cc-pVTZ and B3LYP/cc-pVQZ, we conclude that the B3LYP functional in conjunction with the TZVP basis set is the most useful computational protocol for the assignment of experimental hfcc's, not only for nuclei of first and second rows, but also for those of the third row.Keywords
This publication has 90 references indexed in Scilit:
- Calculation of the hyperfine constants of phosphorus-containing radicalsMolecular Physics, 1997
- Development and validation of reliable quantum mechanical approaches for the study of free radicals in solutionThe Journal of Chemical Physics, 1996
- Structural and Chemical Properties of Silyl RadicalsChemical Reviews, 1995
- Radical cations in mixtures of phosphorus trichloride and dimethyl sulfide. A combined ESR and quantum chemical studyThe Journal of Physical Chemistry, 1992
- Trapping and ESR study of an allylic radical involving the participation of a phosphoranyl moiety: R3PC.bul.HCR2Journal of the American Chemical Society, 1990
- Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursorsJournal of the American Chemical Society, 1990
- An ESR study on electron‐capture phosphorus‐centred radicals in solid matrices of alkyl/phenyl phosphine sulfides and selenidesRecueil des Travaux Chimiques des Pays-Bas, 1989
- Free-radical reactions of organophosphorus compounds. 10. Memory effects in alkoxy-radical oxidations of trialkyl phosphites. Alkoxy group equivalence in (RO)4P.cntdot., a reexaminationJournal of the American Chemical Society, 1978
- Free-radical reactions of organophosphorus compounds. 9. The question of memory effects in the alkoxy-radical oxidations of cyclic trivalent phosphorus derivativesJournal of the American Chemical Society, 1978
- Ligand electronegativity effect on the spin distribution in phosphoranyl radicalsJournal of the American Chemical Society, 1975