OH Roaming during the Ozonolysis of α-Pinene: A New Route to Highly Oxygenated Molecules?

Collection on the Spectroscopy, Structure, and Reactivity of Stabilized Criegee Intermediates

“…These decomposition mechanisms show rich dynamics, including quantum-mechanical tunnelling and large-amplitude “roaming” rearrangements. Computational chemistry has played an important role in unravelling these mechanisms, , and in computing both microcanonical and thermal rate coefficients that can approach quantitative agreement with the experimental data provided tunnelling is correctly incorporated …”

“…Not only is there fundamental interest in the structural and conformer dependence of the bimolecular reaction rates, but many of the studies of the rates of these bimolecular reactions are also motivated by their potential importance in atmospheric oxidation chemistry. This chemistry is thought to be particularly significant in forested regions where biogenic emissions of isoprene and other unsaturated organic compounds are high, and their ozonolysis reactions are a localized source of sCIs. ,,,, The atmospheric significance of sCI chemistry also extends to reactions in aqueous solution, such as in aerosols comprising water droplets dispersed in air, or at the surfaces of these droplets. − Both the gas-phase reactions of sCIs that produce highly oxygenated organic compounds with low vapor pressures and condensed phase reactions in or on water droplets are plausible routes to growth of secondary organic aerosol particles in the troposphere …”