| Téléchargement | - Voir le manuscrit accepté : Kinetics of the addition of olefins to Si-centered radicals: The critical role of dispersion interactions revealed by theory and experiment (PDF, 785 Kio)
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| DOI | Trouver le DOI : https://doi.org/10.1021/acs.jpca.5b03251 |
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| Auteur | Rechercher : Johnson, Erin R.; Rechercher : Clarkin, Owen J.; Rechercher : Dale, Stephen G.; Rechercher : Dilabio, Gino A.1 |
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| Affiliation | - Conseil national de recherches du Canada. Institut national de nanotechnologie
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| Format | Texte, Article |
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| Sujet | Addition reactions; Density functional theory; Electromagnetic dispersion; Functional groups; Kinetics; Olefins; Photolysis; Competition kinetic; Dispersion correction; Dispersion interaction; Laser flash photolysis; Silyl radical; Solution phase; Transition state; Trimethylsilyl; Rate constants |
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| Résumé | Solution-phase rate constants for the addition of selected olefins to the triethylsilyl and tris(trimethylsilyl)silyl radicals are measured using laser-flash photolysis and competition kinetics. The results are compared with predictions from density functional theory (DFT) calculations, both with and without dispersion corrections obtained from the exchange-hole dipole moment (XDM) model. Without a dispersion correction, the rate constants are consistently underestimated; the errors increase with system size, up to 106 s-1 for the largest system considered. Dispersion interactions preferentially stabilize the transition states relative to the separated reactants and bring the DFT-calculated rate constants into excellent agreement with experiment. Thus, dispersion interactions are found to play a key role in determining the kinetics for addition reactions, particularly those involving sterically bulky functional groups. |
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| Date de publication | 2015-05-07 |
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| Dans | |
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| Langue | anglais |
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| Publications évaluées par des pairs | Oui |
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| Numéro NPARC | 21275827 |
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| Exporter la notice | Exporter en format RIS |
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| Signaler une correction | Signaler une correction (s'ouvre dans un nouvel onglet) |
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| Identificateur de l’enregistrement | 066fef25-a2bb-4a8a-aa1a-99ceabca849a |
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| Enregistrement créé | 2015-07-14 |
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| Enregistrement modifié | 2020-06-04 |
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