Enhanced ClNO$_2$ formation at the interface of sea-salt aerosol

Seokjin Moon; David T. Limmer

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arXiv · 2403.09052

Enhanced ClNO$_2$ formation at the interface of sea-salt aerosol

Seokjin Moon·David T. Limmer

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Abstract

The reactive uptake of $\mathrm{N_2O_5}$ on sea-spray aerosol plays a key role in regulating NO$_\mathrm{x}$ 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 $\mathrm{N_2O_5}$ to form ClNO$_2$, the primary reactive channel within sea-spray aerosol. We find the formation of ClNO$_2$ 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 $\mathrm{N_2O_5}$ 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.

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Seokjin Moon, David T. Limmer. 2024-03-14. Enhanced ClNO$_2$ formation at the interface of sea-salt aerosol. https://arxiv.org/abs/2403.09052

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