Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals

Baptiste Sirjean (1) , Pierre-Alexandre Glaude (1) , M.F. Ruiz-Lopez (2) , René Fournet (1)

1 DCPR - Département de Chimie Physique des Réactions
2 SRSMC - Structure et Réactivité des Systèmes Moléculaires Complexes

While many studies have been reported on the reactions of aliphatic hydrocarbons, the chemistry of cyclic hydrocarbons has not been explored extensively. In the present work, a theoretical study of the gas-phase unimolecular decomposition of cyclic alkyl radicals was performed by means of quantum chemical calculations at the CBS-QB3 level of theory. Energy barrier and high-pressure limit rate constants were calculated systematically. Thermochemical data were obtained from isodesmic reactions and the contribution of hindered rotors was taken into account. Classical transition state ...

Mots clés: Cyclic alkyl radicals; beta-scission; combustion; thermal decomposition; kinetic modeling; CBS-QB3; theoretical calculations; rate parameters; thermochemical data; ring strain energy; AIM.; AIM

Domaines: Chimie-Physique [physics.chem-ph]

Baptiste Sirjean, Pierre-Alexandre Glaude, M.F. Ruiz-Lopez, René Fournet. Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals. Journal of Physical Chemistry A, 2008, 112 (46), pp.11598-11610. ⟨hal-00341975⟩