| Download | - View accepted manuscript: Kinetics of the addition of olefins to Si-centered radicals: The critical role of dispersion interactions revealed by theory and experiment (PDF, 785 KiB)
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| DOI | Resolve DOI: https://doi.org/10.1021/acs.jpca.5b03251 |
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| Author | Search for: Johnson, Erin R.; Search for: Clarkin, Owen J.; Search for: Dale, Stephen G.; Search for: Dilabio, Gino A.1 |
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| Affiliation | - National Research Council of Canada. National Institute for Nanotechnology
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| Format | Text, Article |
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| Subject | 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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| Abstract | 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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| Publication date | 2015-05-07 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21275827 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | 066fef25-a2bb-4a8a-aa1a-99ceabca849a |
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| Record created | 2015-07-14 |
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| Record modified | 2020-06-04 |
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