Dynamics of the reactions of O(1D) with CD3OH and CH3OD studied with time-resolved Fourier-transform IR spectroscopy.

We investigated the reactivity of O((1)D) towards two types of hydrogen atoms in CH(3)OH. The reaction was initiated on irradiation of a flowing mixture of O(3) and CD(3)OH or CH(3)OD at 248 nm. Relative vibration-rotational populations of OH and OD (1 ≤ v ≤ 4) states were determined from their infrared emission recorded with a step-scan time-resolved Fourier-transform spectrometer. In O((1)D) + CD(3)OH, the rotational distribution of OD is nearly Boltzmann, whereas that of OH is bimodal; the product ratio [OH]/[OD] is 1.56 ± 0.36. In O((1)D) + CH(3)OD, the rotational distribution of OH is nearly Boltzmann, whereas that of OD is bimodal; the product ratio [OH]/[OD] is 0.59 ± 0.14. Quantum-chemical calculations of the potential energy and microcanonical rate coefficients of various channels indicate that the abstraction channels are unimportant and O((1)D) inserts into the C-H and O-H bonds of CH(3)OH to form HOCH(2)OH and CH(3)OOH, respectively. The observed three channels of OH are consistent with those produced via decomposition of the newly formed OH or the original OH moiety in HOCH(2)OH or decomposition of CH(3)OOH. The former decomposition channel of HOCH(2)OH produces vibrationally more excited OH because of incomplete intramolecular vibrational relaxation, and decomposition of CH(3)COOH produces OH with greater rotational excitation, likely due to a large torque angle during dissociation. The predicted [OH]/[OD] ratios are 1.31 and 0.61 for O((1)D) + CD(3)OH and CH(3)OD, respectively, at collision energy of 26 kJ mol(-1), in satisfactory agreement with the experimental results. These predicted product ratios vary weakly with collision energy.