HIOx–IONO2 Dynamics at the Air–Water Interface: Revealing the Existence of a Halogen Bond at the Atmospheric Aerosol Surface

Iodine is enriched in marine aerosols, particularly in coastal mid-latitude atmospheric environments, where it initiates the formation of new aerosol particles with iodic acid (HIO3) composition. However, particle formation in polluted and semipolluted locations is inhibited when the iodine monoxide radical (IO) is intercepted by NO2 to form the iodine nitrate (IONO2). The primary fate of IONO2 is believed to be, besides photolysis, uptake by aerosol surfaces, leading to particulate iodine activation. Herein we have performed Born-Oppenheimer molecular dynamics (BOMD) simulations and gas-phase quantum chemical calculations to study the iodine acids-iodine nitrate [HIOx (x = 2 and 3)-IONO2] dynamics at the air-water interface modeled by a water droplet of 191 water molecules. The results indicate that IONO2 does not react directly with these iodine acids, but forms an unusual kind of interaction with them within a few picoseconds, which is characterized as halogen bonding. The halogen bond-driven HIO3-IONO2 complex at the air-water interface undergoes deprotonation and exists as IO3--IONO2 anion, whereas the HIO2-IONO2 complex does not exhibit any proton loss to the interfacial water molecules. The gas-phase quantum chemical calculations suggest that the HIO3-IONO2 and HIO2-IONO2 complexes have appreciable stabilization energies, which are significantly enhanced upon deprotonation of iodine acids, indicating that these halogen bonds are fairly stable. These IONO2-induced halogen bonds explain the rapid loss of IONO2 to background aerosol. Moreover, they appear to work against iodide formation. Thus, they may play an important role in enhancing the amount of atmospherically nonrecyclable iodine (iodate) in marine aerosol. © 2020 American Chemical SocietyThis work was supported by the University of Nebraska Holland Computing Center.Peer reviewe