title: Theoretical study of the reaction of CH3 with HOCO radicals.
abstract: The reaction of HOCO radicals with CH3 radicals is examined using the coupled cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the CH3 + HOCO reaction can produce both the H2O + CH2CO and the CH4 + CO2 products through acetic acid and enediol intermediates. Direct ab initio dynamics calculations determine the thermal rate coefficients to be k(T/K) = 3.24 x 10(-11)T0.1024 in cm3 x molec(-1) x s(-1) at T </= 1000 K for the overall reaction. In addition, the product branching ratio of (H2O + CH2CO) to (CH4 + CO2) is predicted to be RH2O/CH4(T/K) = 1.52 + (1.95 x 10(-4))T using RRKM theory. Both the thermal rate coefficients and the product branching ratios are weakly temperature dependent.
authors.affiliation: Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973-5000, USA. francisc@purdue.edu
authors.forename: Hua-Gen
authors.initials: HG
authors.lastname: Yu