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DOI	10.5194/acp-22-14529-2022
	Oligomer formation from the gas-phase reactions of Criegee intermediates with hydroperoxide esters: mechanism and kinetics
	Chen, Long; Huang, Yu; Xue, Yonggang; Jia, Zhihui; Wang, Wenliang
发表日期	2022
ISSN	1680-7316
EISSN	1680-7324
起始页码	14529
结束页码	14546
卷号	22 期号:22 页码:18
英文摘要	Hydroperoxide esters, formed in the reactions of carbonyl oxides (also called Criegee intermediates, CIs) with formic acid, play a crucial role in the formation of secondary organic aerosol (SOA) in the atmosphere. However, the transformation mechanism of hydroperoxide esters in the presence of stabilized Criegee intermediates (SCIs) is not well understood. Herein, the oligomerization reaction mechanisms and kinetics of distinct SCI (CH2OO, syn-CH3CHOO, anti-CH3CHOO, and (CH3)(2)COO) reactions, with their respective hydroperoxide esters and with hydroperoxymethyl formate (HPMF), are investigated in the gas phase using quantum chemical and kinetics modeling methods. The calculations show that the addition reactions of SCIs with hydroperoxide esters proceed through successive insertion of SCIs into hydroperoxide ester to form oligomers that involve SCIs as the repeated chain unit. The saturated vapor pressure and saturated concentration of the formed oligomers decrease monotonically as the number of SCIs is increased. The exothermicity of oligomerization reactions decreases significantly when the number of methyl substituents increases, and the exothermicity of anti-methyl substituted carbonyl oxides is obviously higher than that of syn-methyl substituted carbonyl oxides. The -OOH insertion reaction is energetically more feasible than the -CH insertion pathway in the SCI oligomerization reactions, and the barrier heights increase with increasing the number of SCIs added to the oligomer, except for syn-CH3CHOO. For the reactions of distinct SCIs with HPMF, the barrier of the -OOH insertion pathway shows a dramatic decrease when a methyl substituent occurs at the anti-position, while it reveals a significant increase when a methyl group is introduced at the syn-position and dimethyl substituent. Compared with the rate coefficients of the CH2OO + HPMF reaction, the rate coefficients increase by about 1 order of magnitude when a methyl substituent occurs at the anti-position, whereas the rate coefficients decrease by 1-2 orders of magnitude when a methyl group is introduced at the syn-position. These new findings advance our current understanding of the influence of Criegee chemistry on the formation and growth processes and the chemical compositions of SOA.
学科领域	Environmental Sciences; Meteorology & Atmospheric Sciences
语种	英语
WOS研究方向	Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
WOS记录号	WOS:000886479500001
来源期刊	ATMOSPHERIC CHEMISTRY AND PHYSICS
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/272982
作者单位	Chinese Academy of Sciences; Institute of Earth Environment, CAS; Shaanxi Normal University; Shaanxi Normal University
推荐引用方式 GB/T 7714	Chen, Long,Huang, Yu,Xue, Yonggang,et al. Oligomer formation from the gas-phase reactions of Criegee intermediates with hydroperoxide esters: mechanism and kinetics[J],2022,22(22):18.
APA	Chen, Long,Huang, Yu,Xue, Yonggang,Jia, Zhihui,&Wang, Wenliang.(2022).Oligomer formation from the gas-phase reactions of Criegee intermediates with hydroperoxide esters: mechanism and kinetics.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(22),18.
MLA	Chen, Long,et al."Oligomer formation from the gas-phase reactions of Criegee intermediates with hydroperoxide esters: mechanism and kinetics".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.22(2022):18.