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• W2317554559 endingPage "3931" @default.
• W2317554559 startingPage "3920" @default.
• W2317554559 abstract "A Cl atom can react with 2,3-dimethylbutane (DMB), 2,3-dimethyl-2-butene (DMBE), and 2,5-dimethyl-2,4-hexadiene (DMHD) in solution via a hydrogen-abstraction reaction. The large exoergicity of the reaction between a Cl atom and alkenes (DMBE and DMHD) makes vibrational excitation of the HCl product possible, and we observe the formation of vibrationally excited HCl (v = 1) for both reactions. In CCl4, the branching fractions of HCl (v = 1), Γ (v = 1), for the Cl-atom reactions with DMBE and DMHD are 0.14 and 0.23, respectively, reflecting an increased amount of vibrational excitation in the products of the more exoergic reaction. In addition, Γ (v = 1) for both reactions is larger in the solvent CDCl3, being 0.23 and 0.40, as the less viscous solvent apparently dampens the vibrational excitation of the nascent HCl less effectively. The bimolecular reaction rates for the Cl reactions with DMB, DMBE, and DMHD in CCl4 are diffusion limited (having rate constants of 1.5 × 10(10), 3.6 × 10(10), and 17.5 × 10(10) M(-1) s(-1), respectively). In fact, the bimolecular reaction rate for Cl + DMHD exceeds a typical diffusion-limited reaction rate, implying that the attractive intermolecular forces between a Cl atom and a C═C bond increase the rate of favorable encounters. The 2-fold increase in the reaction rate of the Cl + DMBE reaction from that of the Cl + DMB reaction likely reflects the effect of the C═C bond, while both the number of C═C bonds and the molecular geometry likely play a role in the large reaction rate of the Cl + DMHD reaction." @default.
• W2317554559 created "2016-06-24" @default.
• W2317554559 creator A5003254841 @default.
• W2317554559 creator A5038696287 @default.
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• W2317554559 date "2016-04-14" @default.
• W2317554559 modified "2023-09-23" @default.
• W2317554559 title "Comparative Study of Cl-Atom Reactions in Solution Using Time-Resolved Vibrational Spectroscopy" @default.
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• W2317554559 doi "https://doi.org/10.1021/acs.jpcb.6b01765" @default.
• W2317554559 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/27046419" @default.
• W2317554559 hasPublicationYear "2016" @default.
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