Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces.

Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born-Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH CHOO at the air-water interface. They show that unlike the simplest Criegee intermediate (CH OO), both syn- and anti-CH CHOO remain inert towards reaction with water. The unexpected high stability of C Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee-water reaction. The simulation of the larger Criegee intermediates, (CH ) COO, syn- and anti-CH C(CH )C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air-water interface.