High-Accuracy Extrapolated Ab Initio Thermochemistry of the Vinyl, Allyl, and Vinoxy Radicals
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Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry, The University of Texas at Austin, 105 E. 24th St., A5300, Austin, Texas 78712-0165, United States
*E-mail: [email protected] (M.E.H.), [email protected] (J.F.S.).
Abstract
Enthalpies of formation at both 0 and 298 K were calculated according to the HEAT (High-accuracy Extrapolated Ab initio Thermochemistry) protocol for the title molecules, all of which play important roles in combustion chemistry. At the HEAT345-(Q) level of theory, recommended enthalpies of formation at 0 K are 301.5 ± 1.3, 180.3 ± 1.8, and 23.4 ± 1.5 kJ mol–1 for vinyl, allyl, and vinoxy, respectively. At 298 K, the corresponding values are 297.3, 168.6, and 16.1 kJ mol–1, with the same uncertainties. The calculated values for the three radicals are in excellent agreement with the corresponding experimental values, but the uncertainties associated with the HEAT values for vinoxy are considerably smaller than those based on experimental studies.
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