Theoretical investigations on the SO2 + HO2 reaction and the SO2–HO2 radical complex

The mechanism of the SO2 + HO2 reaction was studied theoretically for the first time. Three product channels were revealed, namely, O2 + HOSO, O2 + HSO2, and OH + SO3. The O2 + HOSO channel dominates the reaction under combustion conditions. A five-member-ring complex [SO2–HO2] exists at the entrance of the reaction. The structure and binding energy (De and D0) of the SO2–HO2 complex have been calculated. In view of D0 = 21.2 ± 2.0 kJ mol−1, the SO2–HO2 complex should be stable at low temperature. The infrared spectra and frequency shifts were calculated for both SO2–HO2 and SO2–DO2, and compared with the available experimental data.