Absolute Determination of the Decomposition Pathways of Electronic Chemically Activated Methanol

Article abstract of DOI:10.1021/j100048a010

Electronic chemically activated methanol was produced in a quasistatic cell in the reaction O(¹D) + CH4<*> -> CH3OH<*>(excit.) at room temperature and pressures in the range 0.5 , OH, and O(³P) were determined with the laser-induced fluorescence (LIF) method.The following product ratios were determined: Φ(OH) = 0.90 (+0.1, -0.2); Φ(CH2O) = 0.06 +/- 0.01; Φ(CH2<*>) = 0.02 +/- 0.01; Φ(O(³P)) = 0.02 +/- 0.01.The concentration profiles of the products CH2O and CH2<*> are in agreement with an overall rate contant of reaction 1 of k₁ = (9 +/- 2) x 10¹³ cm³/mol s, proving CH2O and CH2<*> to be primary products of reaction 1.The bending mode in CH2<*> was found to be excited up to ν₂'' = 1.If the reaction proceeds completely via insertion of the O(¹D) into the C-H bond, the initially formed complex CH3OH(excit.) decomposes with a product distribution which is nonstatistical, i.e., prior to energy randomization.