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| - Photochemical Reaction Dynamics of O(1D) with Saturated Hydrocarbons, CH4, C2H6, andC3H8, under Bulk Conditions and in van der Waals Complexes
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| - The reactions of O(1D) atom with saturatedhydrocarbons (RH), CH4, C2H6, andC3H8, were studied bymonitoring the laser induced fluorescence of products OH in thev‘‘ = 0 and 1 levels under bulk conditionsand in van der Waals complexes, N2O·RH.O(1D) was produced by the ArF excimer laserphotolysis ofN2O. Nascent rotational distributions are bimodal inall cases; the low- and high-N components. Theformeris formed from a long-lived collision complex generated by theinsertion process. The collision complex hasenough lifetime to randomize excess energy before decomposition.The high-N component is produced inthe short-lived insertion process, in which the collision energy ofO(1D) atoms is reflected in the rotationalenergy. The spin−orbit state in the only half-reactionsproducing the v‘‘ = 0 level shows largepopulationin the low-lying 2Π3/2 state inlow-N components, though spin−orbit populations arestatistical in other reactionsystems studied. The reaction proceeds via a transfer from asinglet reaction surface to a triplet surfacekeeping the conservation of the electronic angularmomentum.
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