Computational investigations on the HO2 + CHBr2O2 reaction: mechanisms, products, and atmospheric implications

Abstract

Using quantum chemistry methods, mechanisms and products of the CHBr₂O₂ + HO₂ reaction in the atmosphere were investigated theoretically. Computational result indicates that the dominant product is CHBr₂OOH + O₂ formed on the triplet potential energy surface (PES). While CBr₂O + OH + HO₂ produced on the singlet PES is subdominant to the overall reaction under the typical atmospheric condition below 300 K. Due to higher energy barriers surmounted, other products including CBr₂O₂ + H₂O₂, CBr₂O + HO₃H, CH₂O + HO₃Br, CHBrO + HO₃ + Br, and CHBr₂OH + O₃ make minor contributions to the overall reaction. In the presence of OH radical, CHBr₂OOH generates CHBr₂O₂ and CBr₂O₂ + H₂O subsequently, which enters into new Br-cycle in the atmosphere. The substitution effect of alkyl group and halogens plays negligible roles to the dominant products in the RO₂ + HO₂ (X = H, CH₃, CH₂OH, CH₂F, CH₂Cl, CH₂Br, CH₂Cl, and CH₂Br) reactions in the atmosphere.

Keywords: Atmospheric reaction; CHBr2O2; HO2; Halogen effect; Mechanisms.