Directional Proton Transfer in the Reaction of the Simplest Criegee Intermediate with Water Involving the Formation of Transient H₃O⁺

The reaction of Criegee intermediates with water vapor has been widely known as a key Criegee reaction in the troposphere. Herein, we investigated the reaction of the smallest Criegee intermediate, CH₂OO, with a water cluster through fragment-based ab initio molecular dynamics simulations at the MP2/aug-cc-pVDZ level. Our results show that the CH₂OO–water reaction could occur not only at the air/water interface but also inside the water cluster. Moreover, more than one reactive water molecules are required for the CH₂OO–water reaction, which is always initiated from the Criegee carbon atom and ends at the terminal Criegee oxygen atom via a directional proton transfer process. The observed reaction pathways include the loop-structure-mediated and stepwise mechanisms, and the latter involves the formation of transient H₃O⁺. The lifetime of transient H₃O⁺ is on the order of a few picoseconds, which may impact the atmospheric budget of the other trace gases in the actual atmosphere.