1. Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation
- Author
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Rongjie Zhang, Hong-Bin Xie, Fangfang Ma, Jingwen Chen, Siddharth Iyer, Mario Simon, Martin Heinritzi, Jiali Shen, Yee Jun Tham, Theo Kurtén, Douglas R. Worsnop, Jasper Kirkby, Joachim Curtius, Mikko Sipilä, Markku Kulmala, Xu-Cheng He, Tampere University, Physics, Institute for Atmospheric and Earth System Research (INAR), Polar and arctic atmospheric research (PANDA), INAR Physical Chemistry, Department of Chemistry, and Department of Physics
- Subjects
MECHANISM ,Health Physics and Radiation Effects ,particle formation ,iodic acid ,iodous acid ,116 Chemical sciences ,AMINES ,General Chemistry ,OXIDATION ,114 Physical sciences ,atmospheric cluster dynamics simulation ,SULFURIC-ACID ,ATMOSPHERIC PARTICLES ,METHANESULFONIC-ACID ,GROWTH ,WATER ,Environmental Chemistry ,AEROSOL FORMATION ,iodine oxoacid nucleation ,quantum chemical calculation ,Chemical Physics and Chemistry - Abstract
Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n(m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2binds more strongly with HIO3and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2clusters rather than for pure HIO3or HIO2ones. Our calculations reveal that the strong binding results from HIO2exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)nclusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2could facilitate the nucleation of other acids beyond HIO3in regions where base vapors such as ammonia or amines are scarce. publishedVersion
- Published
- 2022