A theoretical investigation of the gas-phase oxidation reaction of the saturated tert-butyl radical

作者：Choi Jong Ho^*; Nam Mi Ja; Youn Sung Eui

来源：ChemPhysChem, 2006, 7(12): 2526-2532.

DOI：10.1002/cphc.200600473

• ab initio calculations
• reaction mechanisms
• oxidation
• radicals
• transition states

The radical-adical reaction mechanism and dynamics of ground-state atomic oxygen [O(P-3)] with the saturated tert-butyl radical (t-C4H9) are investigated using the density functional method and the complete basis set model. Two distinctive reaction pathways are predicted to be in competition: addition and abstraction. The barrierless addition of O(P-3) t-C4H9 leads to the formation of an energy-rich intermediate (OC4H9) on the lowest doublet potential energy surface, which undergoes subsequent direct elimination or isomerization-elimination leading to various products: C3H6O + CH3, iso-C4H8O + H, C3H7O + CH2 and iso-C4H8 + OH. The respective microscopic reaction process examined with the aid of statistical calculations predict that the major addition pathway is the formation of acetone (C3H6O) + CH3 through a low barrier, single-step cleavage. For the direct, barrierless H-atom abstraction mechanism producing iso-C4H8 (isobutene) + OH, which was recently reported in gas-phase crossed beam investigations, the reaction is described in terms of both an abstraction process (major) and short-lived addition dynamic complex (minor).

• 出版日期2006-12-11