| Title: | Formation of Substituted Alkyls as Precursors of Peroxy Radicals with a Rapid H-Shift in the Atmosphere |
| Author(s): | Wu X; Huang C; Chai J; Zhang F; |
| Address: | "Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, P. R. China. Chair of Technical Thermodynamics, RWTH Aachen University, 52062 Aachen, Germany. Institute at Brown for Environment and Society, and Department of Earth, Environmental and Planetary Sciences, Brown University, 182 Hope Street, Providence, Rhode Island 02912, United States" |
| DOI: | 10.1021/acs.jpclett.1c02503 |
| ISSN/ISBN: | 1948-7185 (Electronic) 1948-7185 (Linking) |
| Abstract: | "Long straight-chain alkyl peroxy (ROO) radicals substituted with C horizontal lineC and oxo functional groups are expected to undergo a rapid hydrogen shift (H-shift), which is a critical step in the atmospheric autoxidation mechanism. The existence of a weak tertiary C-H bond plays a key role in the rapid H-shift. Here, the reaction kinetics between OH and two typical long straight-chain functionalized volatile organic compounds, 3-methyl-1-hexene (3-MH) and 2-methylpentanal (2-MP), was theoretically investigated to reveal the fate of the weak C-H bond. The results indicate that the most favored reaction pathways are direct consumption (H-abstraction of 2-MP) and indirect destruction (addition of OH to 3-MH) of the 'weak' tertiary C-H bond. The yields of abstraction pathways producing precursors of ROO radicals that undergo rapid H-shifts are computed to be less than 10% for both 3-MH + OH and 2-MP + OH reactions" |
| Notes: | "PubMed-not-MEDLINEWu, Xiaoqing Huang, Can Chai, Jiajue Zhang, Feng eng 2021/09/08 J Phys Chem Lett. 2021 Sep 16; 12(36):8790-8797. doi: 10.1021/acs.jpclett.1c02503. Epub 2021 Sep 7" |
