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Theoretical Study of the Reaction of CH3 with HOCO Radicals

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journal contribution
posted on 23.04.2009, 00:00 authored by Hua-Gen Yu, Joseph S. Francisco
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 × 10−11T0.1024 in cm3·molec−1·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 × 10−4)T using RRKM theory. Both the thermal rate coefficients and the product branching ratios are weakly temperature dependent.