气候变化领域集成服务门户(CCPortal): OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship

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DOI	10.5194/acp-22-3693-2022
	OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship
	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	3693
结束页码	3711
卷号	22 期号:5 页码:19
英文摘要	Hydroxyalkyl hydroperoxides (HHPs), formed in the reactions of Criegee intermediates (CIs) with water vapor, play essential roles in the formation of secondary organic aerosol (SOA) under atmospheric conditions. However, the transformation mechanisms for the OH-initiated oxidation of HHPs remain incompletely understood. Herein, the quantum chemical and kinetics modeling methods are applied to explore the mechanisms of the OH-initiated oxidation of the distinct HHPs (HOCH2OOH, HOCH(CH3)OOH, and HOC(CH3)(2)OOH) formed from the reactions of CH2OO, anti-CH3CHOO, and (CH3)(2)COO with water vapor. The calculations show that the dominant pathway is H-abstraction from the -OOH group in the initiation reactions of the OH radical with HOCH2OOH and HOC(CH3)(2)OOH. H-abstraction from the -CH group is competitive with that from the -OOH group in the reaction of the OH radical with HOCH(CH3)OOH. The barrier of H-abstraction from the -OOH group slightly increases when the number of methyl groups increase. In pristine environments, the self-reaction of the RO2 radical initially produces a tetroxide intermediate via oxygen-to-oxygen coupling, and then it decomposes into propagation and termination products through asymmetric two-step O-O bond scission, in which the rate-limiting step is the first O-O bond cleavage. The barrier height of the reactions of distinct RO2 radicals with the HO2 radical is not affected by the number of methyl substitutions. In urban environments, the reaction with O-2 to form formic acid and the HO2 radical is the dominant removal pathway for the HOCH2O radical formed from the reaction of the HOCH2OO radical with NO. The beta-site C-C bond scission is the dominant pathway in the dissociation of the HOCH(CH3)O and HOC(CH3)(2)O radicals formed from the reactions of NO with HOCH(CH3)OO and HOC(CH3)(2)OO radicals. These new findings deepen our understanding of the photochemical oxidation of hydroperoxides under realistic atmospheric conditions.
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:000773402200001
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/273621
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. OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship[J],2022,22(5):19.
APA	Chen, Long,Huang, Yu,Xue, Yonggang,Jia, Zhihui,&Wang, Wenliang.(2022).OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(5),19.
MLA	Chen, Long,et al."OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.5(2022):19.