Surface Confinement of Finite-Size Water Droplets for SO₃ Hydrolysis Reaction Revealed by Molecular Dynamics...

As an important source for sulfuric acid in the atmosphere, hydrolysis of sulfur trioxide (SO₃) takes place with water clusters of sizes from several molecules to several nanometers, resulting in various final products, including neutral (H₂SO₄)-(H₂O) clusters and ionic (HSO₄)^--(H₃O)⁺ clusters. The diverse products may be due to the ability of proton transfer and the formation of hydrated ions for water cluster of finite sizes, especially the sub-micrometer ones. However, the detailed molecular-level mechanism is still unclear due to the lack of available characterization and simulations tools. Here, we developed a quantum chemistry-level machine learning (ML) model to simulate the hydrolysis of SO₃ with water clusters of sizes up to nanometers. The simulation results demonstrate diverse reaction paths taking place between SO₃ and water clusters of different sizes. Generally, neutral (H₂SO₄)-(H₂O) clusters are preferred by water clusters of ultra-small size, and a loop structure-mediated mechanism with SO₃(H₂O) structures and a non-loop structure-mediated mechanism with structure relaxation are observed. As the water cluster size increases to (H₂O)₈, a (HSO₄)^--(H₃O)⁺ ion-pair product emerges; and the Eigen-Zundel ion conversion-like proton transfer mechanism takes place and stabilizes the ion pairs. As the water cluster sizes further increase beyond several nanometers ((H₂O)), the (SO₄)^2-[(H₃O)⁺]₂ ion-pair product appears. The reason could be that the surface of these water clusters is large enough to screen Coulomb repulsion between two tri-coordinated ion-pair complexes. These findings would provide new perspectives for understanding SO₃ hydrolysis in the real atmosphere and sulfuric acid chemistry in atmospheric aerosols.