In the present work, the mechanisms, thermochemistry and kinetics of the reaction of SO
2 with O
3− have been studied using the CCSD(T)/6-31G(d) + CF method. It has been shown that there exist two possible pathways A and B of the
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In the present work, the mechanisms, thermochemistry and kinetics of the reaction of SO
2 with O
3− have been studied using the CCSD(T)/6-31G(d) + CF method. It has been shown that there exist two possible pathways A and B of the SO
2 + O
3− → SO
3− + O
2 reaction. The two pathways’ A and B barrier heights are 0.61 kcal mol
−1 and 3.40 kcal mol
−1, respectively, while the energy of the SO
2 + O
3− → SO
3− + O
2 reaction is −25.25 kcal mol
−1. The canonical variational transition state theory with small-curvature tunneling (CVT/SCT) has been applied to study the reaction kinetics. The CVT/SCT study shows that the rate constants K for pathways A and B, K
A = 1.11 × 10
−12exp(−2526.13/T) and K
B = 2.7 × 10
−14exp(−1029.25/T), respectively, grow as the temperature increases and are much larger than those of the SO
2 + O
3 → SO
3 + O
2 reaction over the entire temperature range of 200–1500 K. This indicates that ionization of O
3 and high temperatures are favorable for the SO
2 oxidation via the reaction with ozone. The new data obtained in the present study can be utilized directly for the evaluation of experiments and model predictions concerning SO
2 oxidation and kinetic modeling of gas-phase chemistry of pollutants/nucleation precursors formed in aircraft engines and the Earth’s atmosphere.
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