PHOTODISSOCIATION OF METHYL HYDROPEROXIDE AT 266 NM - VECTOR CORRELATIONS AND ENERGY-DISTRIBUTION IN THE OH FRAGMENT

The energy content and correlation of vectorial properties of the OH fragment photorejected by methyl hydroperoxide (CH3OOH) at 266 nm are probed by laser excitation, polarization, and high-resolution sub-Doppler spectroscopy. The nascent OH is found to be vibrationally cold and the rotational distribution peaks at approximately N = 6. Polarization dependence of the fragment Doppler profiles and nonequilibrium LAMBDA-doublet populations show that, at high rotational energy, the velocity vector of the OH fragment has a preference to be perpendicular to the planes of rotation of the nuclei and the half-filled 2p-pi orbital. The fragment angular distribution indicates that dissociation of the parent excited state is fairly prompt, with a lifetime of approximately 250 fs.