Molecular Interaction and Orientation of HOCl on Aqueous and Ice Surfaces

The interaction and orientation of hypochlorous acid (HOCl) on the ice surface has been of great interest as it has important implications to ozone depletion. As HOCl interacts with the ice surface, previous classical molecular dynamics simulations suggest its OH moiety orients to the outside of the ice surface, whereas the quantum calculations performed at 0 K indicate its Cl atom is exposed. To resolve this contradiction, herein, Born-Oppenheimer molecular dynamics simulations are adopted, and the results suggest that at ambient temperature, the interaction between HOCl with interfacial water is dominated by the robust H-bond of (HOCl)H-O(H₂O). As a result, the HOCl mainly acts as the proton donor to the water surface, which thus can participate in proton transfer reactions via the promotion of interfacial water. Moreover, the Cl atom of HOCl is found to be exposed to the outside of the water surface. Therefore, during the heterogeneous reactions of HOCl on the water surface, the Cl atom becomes the reactive site and is easily attacked by other species.