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The Role of Hydrogen Migrations in Carbonyl Peroxy Radicals in the Atmosphere
王黎明
作者单位E-mail
王黎明 School of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou 510640, China wanglm@scut.edu.cn 
摘要:
Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out here to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ~0.012 and ~0.58 s?1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process; while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.
关键词:  carbonyl radical, hydrogen migration, atmospheric chemistry
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The Role of Hydrogen Migrations in Carbonyl Peroxy Radicals in the Atmosphere
Wang Liming
Abstract:
Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out here to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ~0.012 and ~0.58 s?1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process; while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.
Key words:  carbonyl radical, hydrogen migration, atmospheric chemistry