H. T. Bian, Z. H. Wang, F. Zhang, Z. D. Wang and J. P. Zhu (2015) Unimolecular Reaction Properties for the Long-Chain Alkenyl Radicals. Journal/International Journal Of Chemical Kinetics 47 685-694. [In English]
Web link: http://dx.doi.org/10.1002/kin.20941
Keywords: SET MODEL CHEMISTRY, N-ALKYL RADICALS, AB-INITIO, MULTICHANNEL, DECOMPOSITION, ATMOSPHERIC-PRESSURE, 1-PENTYL RADICALS, LOW-TEMPERATURE, OCTYL RADICALS, SHOCK-TUBE, COMBUSTION
Abstract: Although alkenyl radicals are important intermediates involved in both alkanes and alkenes combustion, previous kinetic studies on them are very limited, especially for the long-chain alkenyl radicals. To deeply investigate unimolecular reaction activities of long-chain alkenyl radicals, a series of octenyl (C8H15) radicals were chosen to study the reaction kinetics of three typical types of reactions (i.e., intramolecular radical addition, internal H-migration, and bond dissociation) in this work. The CBS-QB3 method was used to build potential energy surfaces for these reactions, and the transition state theory was applied to obtain the high-pressure limit rate constants. Some general rules are observed from our systematic calculations in respect of structure-activity relationships. (C) 2015 Wiley Periodicals, Inc. Int J Chem Kinet 47: 685-694, 2015

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