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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry