Kinetics of the addition of olefins to Si-centered radicals: The critical role of dispersion interactions revealed by theory and experiment

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DOIResolve DOI: http://doi.org/10.1021/acs.jpca.5b03251
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TypeArticle
Journal titleJournal of Physical Chemistry A
ISSN1089-5639
Volume119
Issue22
Pages58835888; # of pages: 6
SubjectAddition 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
AbstractSolution-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.
Publication date
PublisherACS Publications
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC); National Institute for Nanotechnology
Peer reviewedYes
NPARC number21275827
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Record identifier066fef25-a2bb-4a8a-aa1a-99ceabca849a
Record created2015-07-14
Record modified2016-05-09
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