Full four-component relativistic calculations of the one-bond 77Se-13C spin-spin coupling constants in the series of selenium heterocycles and their parent open-chain selenides
Copyright © 2014 John Wiley & Sons, Ltd.
| Publié dans: | Magnetic resonance in chemistry : MRC. - 1985. - 52(2014), 5 vom: 18. Mai, Seite 214-21 |
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| Auteur principal: | |
| Autres auteurs: | , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2014
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| Accès à la collection: | Magnetic resonance in chemistry : MRC |
| Sujets: | Journal Article Research Support, Non-U.S. Gov't 77Se NMR 77Se-13C spin-spin coupling constants locally dense basis set open-chain selenides relativistic effects scalar relativistic corrections selenium heterocycles solvent effects plus... |
| Résumé: | Copyright © 2014 John Wiley & Sons, Ltd. Four-component relativistic calculations of (77)Se-(13)C spin-spin coupling constants have been performed in the series of selenium heterocycles and their parent open-chain selenides. It has been found that relativistic effects play an essential role in the selenium-carbon coupling mechanism and could result in a contribution of as much as 15-25% of the total values of the one-bond selenium-carbon spin-spin coupling constants. In the overall contribution of the relativistic effects to the total values of (1)J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin-orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second-order polarization propagator approach (CC2) with the four-component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of (1)J(Se,C). Solvent effects in the values of (1)J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2-78.4) are next to negligible decreasing negative (1)J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of (77)Se-(13)C spin-spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1-0.2-Hz loss of accuracy |
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| Description: | Date Completed 24.11.2014 Date Revised 07.04.2014 published: Print-Electronic Citation Status MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.4053 |