Temperature-dependent kinetics of the atmospheric reaction between CHOO and acetone.

Criegee intermediates are important oxidants produced in the ozonolysis of alkenes in the atmosphere. Quantitative kinetics of the reactions of Criegee intermediates are required for atmospheric modeling. However, the experimental studies do not cover the full relevant range of temperature and pressure. Here we report the quantitative kinetics of CHOO + CHC(O)CH by using our recently developed dual strategy that combines coupled cluster theory with high excitation levels for conventional transition state theory and well validated levels of density functional theory for direct dynamics calculations using canonical variational transition theory including tunneling. We find that the W3X-L//DF-CCSD(T)-F12b/jun-cc-pVDZ electronic structure method can be used to obtain quantitative kinetics of the CHOO + CHC(O)CH reaction. Whereas previous investigations considered a one-step mechanistic pathway, we find that the CHOO + CHC(O)CH reaction occurs in a stepwise manner. This has implications for the modeling of Criegee-intermediate reactions with other ketones and with aldehydes. In the kinetics calculations, we show that recrossing effects of the conventional transition state are negligible for determining the rate constant of CHOO + CHC(O)CH. The present findings reveal that the rate ratio between CHOO + CHC(O)CH and OH + CHC(O)CH has a significant negative dependence on temperature such that the CHOO + CHC(O)CH reaction can contribute as a significant sink for atmospheric CHC(O)CH at low temperature. The present findings should have broad implications in understanding the reactions of Criegee intermediates with carbonyl compounds and ketones in the atmosphere.