Barrierless reactions of C2 Criegee intermediates with H_(2)SO_(4)and their implication to oligomers and new particle formation  

作　　者：Yang Cheng Chao Ding Tianlei Zhang Rui Wang Ruxue Mu Zeyao Li Rongrong Li Juan Shi Chongqin Zhu 

机构地区：[1]Institute of Theoretical and Computational Chemistry,Shaanxi Key Laboratory of Catalysis,School of Chemical&Environment Science,Shaanxi University of Technology,Hanzhong,Shaanxi 723001,China [2]College of Chemistry,Key Laboratory of Theoretical&Computational Photochemistry of Ministry of Education,Beijing Normal University,Beijing 100190,China

出　　处：《Journal of Environmental Sciences》2025年第3期574-584,共11页环境科学学报(英文版)

基　　金：supported by the National Natural Science Foundation of China(Nos.22073059 and 22203052);the Natural Science Foundation of Shaanxi Province(No.2022JM-060);the Education Department of Shaanxi Provincial Government(No.23JC023);the Key Cultivation Project of Shaanxi University of Technology(No.SLG2101)。

摘　　要：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(CH_(3)CHOO)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 CH_(3)CHOO and H_(2)SO_(4)both in the gas phase and at the airwater interface.In the gas phase,the addition reaction of CH_(3)CHOO with H_(2)SO_(4)to generate CH_(3)HC(OOH)OSO_(3)H(HPES)is near-barrierless,regardless of the presence of water molecules.BOMD simulations showthat 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 CH_(3)CHOO with HPES in the gas phase is both thermochemically and kinetically favored.Also,it is noted that the interfacial HPES−ion can attract H_(2)SO_(4),NH_(3),(COOH)_(2)and HNO_(3)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.

关 键 词：Criegee intermediates H_(2)SO_(4) Atmospheric behavior Air-water interface Chemical processes 

分 类 号：O62[理学—有机化学]