Global S&T Development Trend Analysis Platform of Resources and Environment
DOI | 10.5194/acp-20-7429-2020 |
H migration in peroxy radicals under atmospheric conditions | |
Vereecken, Luc1,2,3; Noziere, Barbara4,5 | |
2020-06-26 | |
发表期刊 | ATMOSPHERIC CHEMISTRY AND PHYSICS |
ISSN | 1680-7316 |
EISSN | 1680-7324 |
出版年 | 2020 |
卷号 | 20期号:12页码:7429-7458 |
文章类型 | Article |
语种 | 英语 |
国家 | Belgium; Germany; France |
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 beta-oxo substitutions both endocyclic and exocyclic to the transition state ring; and alpha-oxo (aldehyde), -OH, -OOH, and -ONO2 substitutions, including migration of beta-based hydrogen atoms. Also discussed are -C(=O)OH and -OR substitutions. The SAR allows predictions of rate coefficients k(T) 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. |
领域 | 地球科学 |
收录类别 | SCI-E |
WOS记录号 | WOS:000543796900002 |
WOS关键词 | HYDROGEN SHIFT REACTIONS ; ISOMERIZATION-REACTIONS ; MASS-SPECTROMETRY ; THERMOCHEMICAL KINETICS ; UNIMOLECULAR REACTIONS ; DENSITY FUNCTIONALS ; RATE RULES ; OXIDATION ; MECHANISM ; IMPACT |
WOS类目 | Environmental Sciences ; Meteorology & Atmospheric Sciences |
WOS研究方向 | Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences |
URL | 查看原文 |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/278049 |
专题 | 地球科学 |
作者单位 | 1.Katholieke Univ Leuven, Dept Chem, Celestijnenlaan 200F, B-3000 Leuven, Belgium; 2.Max Planck Inst Chem, Hahn Meitner Weg 1, D-55128 Mainz, Germany; 3.Forschungszentrum Julich, Inst Energy & Climate Res, IEK Troposphere 8, D-52428 Julich, Germany; 4.CNRS, IRCELYON, Ave Albert Einstein 2, F-69626 Villeurbanne, France; 5.Univ Claude Bernard Lyon, Ave Albert Einstein 2, F-69626 Villeurbanne, France |
推荐引用方式 GB/T 7714 | Vereecken, Luc,Noziere, Barbara. H migration in peroxy radicals under atmospheric conditions[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2020,20(12):7429-7458. |
APA | Vereecken, Luc,&Noziere, Barbara.(2020).H migration in peroxy radicals under atmospheric conditions.ATMOSPHERIC CHEMISTRY AND PHYSICS,20(12),7429-7458. |
MLA | Vereecken, Luc,et al."H migration in peroxy radicals under atmospheric conditions".ATMOSPHERIC CHEMISTRY AND PHYSICS 20.12(2020):7429-7458. |
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