Isomer-selective study of the OH-initiated oxidation of isoprene in the presence of O(2) and NO: 2. the major OH addition channel.

We report the first isomeric-selective study of the dominant isomeric pathway in the OH-initiated oxidation of isoprene in the presence of O2 and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photolysis of monodeuterated/nondeuterated 2-iodo-2-methylbut-3-en-1-ol results exclusively in the dominant OH-isoprene addition product, providing important insight into the oxidation mechanism. On the basis of kinetic analysis of OH cycling experiments, we have determined the rate constant for O2 addition to the hydroxyalkyl radical to be 1.0(-0.5)+1.7 x 10(-12) cm3 s(-1), and we find a value of 8.1-2.3+3.4 x 10(-12) cm3 s(-1) for the overall reaction rate constant of the resulting hydroxyperoxy radical with NO. We also report the first clear experimental evidence of the (E) form of the delta-hydroxyalkoxy channel through isotopic labeling experiments and quantify its branching ratio to be (10 +/- 3)%. This puts a rigorous upper limit on the branching of the (E)-delta-hydroxyalkoxy radical channel. Since our measured isomeric-selective rate constants for the dominant outer channel in OH-initiated isoprene chemistry are similar to the overall rate constants derived from nonisomeric kinetics, we predict that the remaining outer addition channel will have similar reactivity.