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Unimolecular Reaction Properties for the Long‐Chain Alkenyl Radicals
Author(s) -
Bian Huiting,
Wang Zhaohui,
Zhang Feng,
Wang Zhandong,
Zhu Jiping
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20941
Subject(s) - chemistry , radical , intramolecular force , dissociation (chemistry) , transition state theory , chain termination , bond dissociation energy , computational chemistry , reaction rate constant , combustion , chain reaction , photochemistry , kinetics , organic chemistry , polymerization , radical polymerization , quantum mechanics , polymer , physics
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 (C 8 H 15 ) 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.