Probing the Exit Channel of the OH + CH 3 OH → H 2 O + CH 3 O Reaction by Photodetachment of CH 3 O - (H 2 O).

Transition state dynamics of bimolecular reactions can be probed by photodetachment of a precursor anion when the Franck-Condon region of the corresponding neutral potential energy surface is near a saddle point. In this study, photodetachment of anions at m / z = 49 enabled investigation of the exit channel of the OH + CH 3 OH → H 2 O + CH 3 O reaction using photoelectron-photofragment coincidence spectroscopy. High-level coupled-cluster calculations of the stationary points on the anion surface show that the methoxide-water cluster CH 3 O - (H 2 O) is the stable minimum on the anion surface. Photodetachment at a 3.20 eV photon energy leads to long-lived H 2 O(CH 3 O) complexes and H 2 O + CH 3 O products consistent with both direct dissociative photodetachment and resonance mediated processes on the neutral surface. The partitioning of total kinetic energy in the system indicates that water stretch and bend excitation is induced in dissociative photodetachment and evidence for long-lived complexes consistent with vibrational Feshbach resonances is reported.