Mechanistic Insights into Criegee Intermediate-Hydroperoxyl Radical Chemistry

The reaction between a Criegee intermediate and the hydroperoxyl radical (HO₂) is believed to play a role in the formation of new particles in the troposphere. Although the reaction has been previously studied in the gas phase, there are several knowledge gaps that still need to be filled. We simulated the reaction of anti-CH₃CHOO with HO₂ and HO₂-H₂O radical complexes in the gas phase at 0 K, which exhibited a low-barrier profile for water-containing systems and a barrierless profile for water-free systems. Moreover, the reaction was found to follow a proton-transfer mechanism, which challenges previous assumptions that the gas-phase reaction involves a hydrogen atom transfer. The HO₂ radical was found to mediate the Criegee hydration reaction in the gas phase. Metadynamics simulations further confirmed that the expected radical adduct formation between anti-CH₃CHOO and the HO₂ radical, as well as the HO₂- and H₂O-mediated reactions in the gas phase, followed a concerted mechanism. By combining constrained ab initio molecular dynamics simulations with thermodynamic integration, we quantitively evaluated the free-energy barriers at high temperatures. The barriers obtained for all three Criegee-HO₂ reaction systems were found to be temperature-dependent. We also compared the free-energy barriers of water-free and water-containing systems; the results revealed that water could hinder the reaction between the Criegee and HO₂ radical. These results suggest that HO₂ radicals may be involved in the formation of tropospheric radical adducts, and water molecules may also play important roles in the reactions of Criegee intermediates.