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Download file# Theoretical Study of the Reaction of CH_{3} with HOCO Radicals

journal contribution

posted on 23.04.2009, 00:00 by Hua-Gen Yu, Joseph S. FranciscoThe reaction of HOCO radicals with CH

_{3}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 CH_{3}+ HOCO reaction can produce both the H_{2}O + CH_{2}CO and the CH_{4}+ CO_{2}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^{−11}*T*^{0.1024}in cm^{3}·molec^{−1}·s^{−1}at*T*≤ 1000 K for the overall reaction. In addition, the product branching ratio of (H_{2}O + CH_{2}CO) to (CH_{4}+ CO_{2}) is predicted to be*R*_{H2O/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.