Role of hydrogen migrations in carbonyl peroxy radicals in the atmosphere
Role of hydrogen migrations in carbonyl peroxy radicals in the atmosphere
复制标题
大气中羰基过氧自由基中氢迁移的作用
DOI：
10.1063/1674-0068/cjcp1811265
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发表时间：
2019-08
影响因子：
1
通讯作者：
Wang Li-ming
中科院分区：
文献类型：
--
作者：
Wang Sai-nan;Wu Run-run;Wang Li-ming
过氧羰基自由基（RC（O）O2）是挥发性有机物大气氧化过程中普遍存在的自由基中间体。本论文通过量子化学和动力学计算，对过氧羰基自由基中单分子氢迁移的作用进行了理论研究。结果表明，至少在CH3CH2CH2C（O）O2和（CH3）2CHCH2C（O）O2中，H-迁移在大气中可能是显著的，在298 K时的速率为~0.012和~0.58 s − 1。 CH3CHCH2C（O）OOH的后续反应会产生多官能团的产物，这可能会影响气溶胶的形成过程;而（CH3）2CCH2C（O）OOH则会在几个步骤中转化为甲醛和丙酮。羰基过氧自由基（carbonyl peroxy radicals，RC（O）O2）是挥发性有机化合物在大气中氧化过程中普遍存在的自由基中间体。本论文通过量子化学和动力学计算，对过氧羰基自由基中单分子氢迁移的作用进行了理论研究。结果表明，至少在CH3CH2CH2C（O）O2和（CH3）2CHCH2C（O）O2中，H-迁移在大气中可能是显著的，在298 K时的速率为~0.012和~0.58 s − 1。 CH3CHCH2C（O）OOH的后续反应会产生多官能团的产物，这可能会影响气溶胶的形成过程;而（CH3）2CCH2C（O）OOH则会在几个步骤中转化为甲醛和丙酮。这些过程对于在低氮氧化物条件下挥发性有机化合物的大气模拟十分重要。
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 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.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 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.
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影响因子：
2.8
作者：
G. L. Zügner;I. Szilágyi;J. Zádor;E. Szabó;S. Dóbé;Xinli Song;Baoshan Wang
通讯作者：
G. L. Zügner;I. Szilágyi;J. Zádor;E. Szabó;S. Dóbé;Xinli Song;Baoshan Wang
影响因子：
1.5
作者：
Roland Gutbrod;S. Meyer;M. Rahman;R. N. Schindler
通讯作者：
Roland Gutbrod;S. Meyer;M. Rahman;R. N. Schindler
DOI：
10.1021/jp1099199
发表时间：
2011-01
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Scott A. Carr;D. Glowacki;Chi-Hsiu Liang;M. Baeza_Romero;M. Blitz;M. Pilling;P. Seakins
通讯作者：
Scott A. Carr;D. Glowacki;Chi-Hsiu Liang;M. Baeza_Romero;M. Blitz;M. Pilling;P. Seakins
影响因子：
1.7
作者：
H. Werner;G. Knizia;F. Manby
通讯作者：
H. Werner;G. Knizia;F. Manby
DOI：
10.1021/jp9098792
发表时间：
2010-04
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Sandeep Sharma;S. Raman;W. Green
通讯作者：
Sandeep Sharma;S. Raman;W. Green