气候变化领域集成服务门户(CCPortal): H migration in peroxy radicals under atmospheric conditions

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DOI	10.5194/acp-20-7429-2020
	H migration in peroxy radicals under atmospheric conditions
	Vereecken L.; Nozière B.
发表日期	2020
ISSN	1680-7316
起始页码	7429
结束页码	7458
卷号	20 期号:12
英文摘要	A large data set of rate coefficients for H migration in peroxy radicals is presented and supplemented with literature data to derive a structure-activity relationship (SAR) for the title reaction class. The SAR supports aliphatic RO2 radicals; unsaturated bonds and iβ/i-oxo substitutions both endocyclic and exocyclic to the transition state ring; and iα/i-oxo (aldehyde), -OH, -OOH, and -ONO2 substitutions, including migration of O-based hydrogen atoms. Also discussed are -C( Combining double low line O)OH and -OR substitutions. The SAR allows predictions of rate coefficients ik/i(iT/i) for a temperature range of 200 to 450 K, with migrations spans ranging from 1,4 to 1,9-H shifts depending on the functionalities. The performance of the SAR reflects the uncertainty of the underlying data, reproducing the scarce experimental data on average to a factor of 2 and the wide range of theoretical data to a factor of 10 to 100, depending also on the quality of the data. The SAR evaluation discusses the performance in multi-functionalized species. For aliphatic RO2, we also present some experimental product identification that validates the expected mechanisms. The proposed SAR is a valuable tool for mechanism development and experimental design and guides future theoretical work, which should allow for rapid improvements of the SAR in the future. Relative multi-conformer transition state theory (rel-MC-TST) kinetic theory is introduced as an aid for systematic kinetic studies. © 2019 Elsevier Ltd. All rights reserved.
语种	英语
scopus关键词	atmospheric chemistry; mercury (element); peroxy radical; reaction kinetics
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/247687
作者单位	Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, Leuven, 3000, Belgium; Max Planck Institute for Chemistry, Hahn-Meitner-Weg 1, Mainz, 55128, Germany; Institute for Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, 52428, Germany; IRCELYON, CNRS and Université Claude Bernard Lyon, Avenue Albert Einstein 2, Villeurbanne, 69626, France
推荐引用方式 GB/T 7714	Vereecken L.,Nozière B.. H migration in peroxy radicals under atmospheric conditions[J],2020,20(12).
APA	Vereecken L.,&Nozière B..(2020).H migration in peroxy radicals under atmospheric conditions.ATMOSPHERIC CHEMISTRY AND PHYSICS,20(12).
MLA	Vereecken L.,et al."H migration in peroxy radicals under atmospheric conditions".ATMOSPHERIC CHEMISTRY AND PHYSICS 20.12(2020).