Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, China.
Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, China.
J Environ Sci (China). 2025 Mar;149:574-584. doi: 10.1016/j.jes.2023.12.020. Epub 2023 Dec 27.
The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol (SOA). However, to date, the reactivity of C2 Criegee intermediates (CHCHOO) in areas contaminated with acidic gas remains poorly understood. Herein, high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations are used to explore the reaction of CHCHOO and HSO both in the gas phase and at the air-water interface. In the gas phase, the addition reaction of CHCHOO with HSO to generate CHHC(OOH)OSOH (HPES) is near-barrierless, regardless of the presence of water molecules. BOMD simulations show that the reaction at the air-water interface is even faster than that in the gas phase. Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids, ammonias, and water molecules to form stable clusters, meanwhile the oligomerization reaction of CHCHOO with HPES in the gas phase is both thermochemically and kinetically favored. Also, it is noted that the interfacial HPES ion can attract HSO, NH, (COOH) and HNO for particle formation from the gas phase to the water surface. Thus, the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions, but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.
Criegee 中间体引发的低聚过氧化氢的形成可能对二次有机气溶胶（SOA）的形成和增长有重要贡献。然而，迄今为止，在受酸性气体污染的地区，C2 Criegee 中间体（CHCHOO）的反应性仍知之甚少。在此，我们使用高精度量子化学计算和 Born-Oppenheimer 分子动力学（BOMD）模拟来探索 CHCHOO 和 HSO 在气相和空气-水界面上的反应。在气相中，CHCHOO 与 HSO 的加成反应生成 CHHC(OOH)OSOH（HPES）几乎是无势垒的，无论是否存在水分子。BOMD 模拟表明，空气-水界面上的反应甚至比气相中的反应更快。进一步的计算表明，HPES 有与硫酸、氨和水分子聚集形成稳定簇的趋势，同时气相中 CHCHOO 与 HPES 的齐聚反应在热化学和动力学上都是有利的。此外，还注意到气相中的界面 HPES 离子可以吸引 HSO、NH、（COOH）和 HNO，从而促进气相到水表面的颗粒形成。因此，这项工作的结果不仅阐明了污染地区 C2 Criegee 中间体的高大气反应性，还加深了我们对 Criegee 中间体诱导大气 SOA 形成过程的理解。
