Two Pathways for Dissociation of Highly Energized <i>syn</i>-CH<sub>3</sub>CHOO to OH Plus Vinoxy
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Abstract
Ozonolysis
of alkenes is an important nonphotolytic source of hydroxl
radicals in the troposphere. The reaction proceeds through cycloaddition
and subsequent decomposition to a carbonyl oxide, known as Criegee
intermediates. Ozonolysis of alkene releases about 50 kcal/mol excess
energy to form highly energized Criegee molecules, which can be stabilized
and undergo further reaction or dissociate to OH+vinoxy products.
The dissociation dynamics of partially stabilized Criegee (<i>syn</i>-CH<sub>3</sub>CHOO) has been thoroughly studied recently,
in which the molecules dissociate by first isomerizing to vinyl hydroperoxide
(VHP). Here we examine the dissociation dynamics of highly energized <i>syn</i>-CH<sub>3</sub>CHOO (42 kcal/mol), and a second, prompt
dissociation path is discovered. The dissociation dynamics of these
two paths are carefully examined through the animation of trajectories
and the energy distributions of products. The new prompt path reveals
a distinctly different translational energy and internal energy distributions
of products compared to the known path through VHP