Photosensitization reactions are believed to provide a key contribution to the overall oxidation chemistry of the Earth's atmosphere. Generally, these processes take place on the surface of aqueous aerosols, where organic surfactants accumulate and react, either directly or indirectly, with the activated photosensitizer. However, the mechanisms involved in these important interfacial phenomena are still poorly known. This work sheds light on the reaction mechanisms of the photosensitizer imidazole-2-carboxaldehyde through ab initio (QM/MM) molecular dynamics simulations and high-level ab initio calculations. The nature of the lowest excited states of the system (singlets and triplets) is described in detail for the first time in the gas phase, in bulk water, and at the air-water interface, and possible intersystem crossing mechanisms leading to the reactive triplet state are analyzed. Moreover, the reactive triplet state is shown to be unstable at the air-water surface in a pure water aerosol. The combination of this finding with the results obtained for simple surfactant-photosensitizer models, together with experimental data from the literature, suggests that photosensitization reactions assisted by imidazole-2-carboxaldehyde at the surface of aqueous droplets can only occur in the presence of surfactant species, such as fatty acids, that stabilize the photoactivated triplet at the interface. These findings should help the interpretation of field measurements and the design of new laboratory experiments to better understand atmospheric photosensitization processes.
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