Abstract
Accurately characterizing isoprene ozonolysis continues to challenge atmospheric chemists. The reaction is believed to be a spontaneous, concerted cycloaddition. However, little information is available about the entrance channel and isoprene-ozone complexes thought to define the long-range portion of the reaction coordinate. Our coupled cluster and auxiliary field quantum Monte Carlo calculations predict multiple stable isoprene-ozone van der Waals complexes for trans-isoprene in the gas phase with moderate association energies. These results indicate that long-range dynamics in the isoprene-ozone entrance channel can impact the overall reaction in the troposphere and provide the spectroscopic information necessary to extend the microwave characterization of isoprene ozonolysis to prereactive complexes. At the air-water interface, Born-Oppenheimer molecular dynamics simulations indicate that the cycloaddition reaction between ozone and trans-isoprene follows a stepwise mechanism, which is quite distinct from our proposed gas-phase mechanism and occurs on a femtosecond time scale. The stepwise nature of isoprene ozonolysis on the aqueous surface is more consistent with the DeMore mechanism than with the Criegee mechanism suggested by the gas-phase calculations, suggesting that the reaction media may play an important role in the reaction. Overall, these predictions aim to provide a missing fundamental piece of molecular insight into isoprene ozonolysis, which has broad tropospheric implications due to its critical role as a nighttime source of hydroxyl radicals.