Reaction of SO3 with HONO2 and Implications for Sulfur Partitioning in the Atmosphere

Sulfur trioxide is a critical intermediate for the sulfur cycle and the formation of sulfuric acid in the atmosphere. The traditional view is that sulfur trioxide is removed by water vapor in the troposphere. However, the concentration of water vapor decreases significantly with increasing altitude, leading to longer atmospheric lifetimes of sulfur trioxide. Here, we utilize a dual-level strategy that combines transition state theory calculated at the W2X//DF-CCSD(T)-F12b/jun'-cc-pVDZ level, with variational transition state theory with small-curvature tunneling from direct dynamics calculations at the M08-HX/MG3S level. We also report the pressure-dependent rate constants calculated using the system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory. The present findings show that falloff effects in the SO₃ + HONO₂ reaction are pronounced below 1 bar. The SO₃ + HONO₂ reaction can be a potential removal reaction for SO₃ in the stratosphere and for HONO₂ in the troposphere, because the reaction can potentially compete well with the SO₃ + 2H₂O reaction between 25 and 35 km, as well as the OH + HONO₂ reaction. The present findings also suggest an unexpected new product from the SO₃ + HONO₂ reaction, which, although very short-lived, would have broad implications for understanding the partitioning of sulfur in the stratosphere and the potential for the SO₃ reaction with organic acids to generate organosulfates without the need for heterogeneous chemistry.