Significant influence of water molecules on the SO₃ + HCl reaction in the gas phase and at the air-water interface

The products resulting from the reactions between atmospheric acids and SO3 have a catalytic effect on the formation of new particles in aerosols. However, the SO3 + HCl reaction in the gas-phase and at the air-water interface has not been considered. Herein, this reaction was explored exhaustively by using high-level quantum chemical calculations and Born Oppenheimer molecular dynamics (BOMD) simulations. The quantum calculations show that the gas-phase reaction of SO3 + HCl is highly unlikely to occur under atmospheric conditions with a high energy barrier of 22.6 kcal mol(-1). H2O and (H2O)(2) play obvious catalytic roles in reducing the energy barrier of the SO3 + HCl reaction by over 18.2 kcal mol(-1). The atmospheric lifetimes of SO3 show that the (H2O)(2)-assisted reaction dominates over the H2O-assisted reaction within the altitude range of 0-5 km, whereas the H2O-assisted reaction is more favorable within an altitude range of 10-50 km. BOMD simulations show that H2O-induced formation of the ClSO3-MIDLINE HORIZONTAL ELLIPSISH3O+ ion pair and HCl-assisted formation of the HSO4-MIDLINE HORIZONTAL ELLIPSISH3O+ ion pair were identified at the air-water interface. These routes followed a stepwise reaction mechanism and proceeded at a picosecond time scale. Interestingly, the formed ClSO3H in the gas phase has a tendency to aggregate with sulfuric acids, ammonias, and water molecules to form stable clusters within 40 ns simulation time, while the interfacial ClSO3- and H3O+ can attract H2SO4, NH3, and HNO3 for particle formation from the gas phase to the water surface. Thus, this work will not only help in understanding the SO3 + HCl reaction driven by water molecules in the gas-phase and at the air-water interface, but it will also provide some potential routes of aerosol formation from the reaction between SO3 and inorganic acids.