Enhanced ClNO₂ Formation at the Interface of Sea-Salt Aerosol

The reactive uptake of N₂O₅ on sea-spray aerosol plays a key role in regulating the NO_<i>x</i> concentration in the troposphere. Despite numerous field and laboratory studies, a microscopic understanding of its heterogeneous reactivity remains unclear. Here, we use molecular simulation and theory to elucidate the chlorination of N₂O₅ to form ClNO₂, the primary reactive channel within sea-spray aerosol. We find that the formation of ClNO₂ is markedly enhanced at the air-water interface due to the stabilization of the charge-delocalized transition state, as evident from the formulation of bimolecular rate theory in heterogeneous environments. We explore the consequences of the enhanced interfacial reactivity in the uptake of N₂O₅ using numerical solutions of molecular reaction-diffusion equations as well as their analytical approximations. Our results suggest that the current interpretation of aerosol branching ratios needs to be revisited.