Formation mechanism of typical aromatic sulfuric anhydrides and their potential role in atmospheric nucleation process  

作　　者：Haijie Zhang Rui Gao Hong Li Yunfeng Li Yisheng Xu Fahe Chai 

机构地区：[1]State Key Laboratory of Environmental Criteria and Risk Assessment,Chinese Research Academy of Environmental Sciences,Beijing 100012,China

出　　处：《Journal of Environmental Sciences》2023年第1期54-64,共11页环境科学学报（英文版）

基　　金：supported by the China Postdoctoral Science Foundation(No.2020M680636);the National Natural Sci-ence Foundation of China(No.41375133);the Science Foundation of Chinese Research Academy of Environmental Sciences(No.JY-41375133);the Beijing Municipal Science&Technology Commission(No.Z181100005418015);the National Key Research and Development Program of China(No.2019YFC0214800)。

摘　　要：Sulfuric anhydrides,generated from the cycloaddition reaction of SO3with carboxylic acids,have been revealed to be potential participants in the nucleation process of new particle formation(NPF).Hence the reaction mechanisms of typical aromatic acids(benzoic acid(BA),phenylacetic acid(PAA),phthalic acid(PA),isophthalic acid(mPA),and terephthalic acid(PTA))with SO3to generate the corresponding aromatic sulfuric anhydrides were investigated by density functional theory calculations at the level of M06-2X/6-311++G(3df,3pd).As a result,these reactions were found to be feasible in the gas phase with barriers of 0.34,0.30,0.18,0.08 and 0.12 kcal/mol to generate corresponding aromatic sulfuric anhydrides,respectively.The thermodynamic stabilities of clusters containing aromatic sulfuric anhydrides and atmospheric nucleation precursors(sulfuric acid,ammonia and dimethylamine)were further analyzed to identify the potential role of aromatic sulfuric anhydrides in NPF.As the thermodynamic stability of a cluster depends on both the number and strength of hydrogen bonds,the greater stability of the interactions between atmospheric nucleation precursors and aromatic sulfuric anhydrides than with aromatic acids make aromatic sulfuric anhydrides potential participators in the nucleation process of NPF.Moreover,compared with BA,the addition of a-CH_(2)-functional group in PAA has little influence on the reaction barrier with SO3but an inhibitive effect on the thermodynamic stability of clusters.The position of the two-COOH functional groups in PA,m PA and PTA does not have a consistent impact on the reaction barrier with SO3or the thermodynamic stability.

关 键 词：New particle formation(NPF) Sulfuric anhydride Reaction mechanism Atmospheric clusters Thermodynamic stability 

分 类 号：X51[环境科学与工程—环境工程]