Computational study on the mechanism and kinetics for the reaction between HO 2 and n -propyl peroxy radical

• Published in: RSC advances Vol. 9; no. 69; pp. 40437 - 40444
• Main Authors: Yang, Zhenli, Lin, Xiaoxiao, Zhou, Jiacheng, Hu, Mingfeng, Gai, Yanbo, Zhao, Weixiong, Long, Bo, Zhang, Weijun
• Format: Journal Article
• Language: English
• Published: England 06.12.2019
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/C9RA07503H

The -propyl peroxy radical ( -C H O ) is the key intermediate during atmospheric oxidation of propane (C H ) which plays an important role in the carbon and nitrogen cycles in the troposphere. In this paper, a comprehensive theoretical study on the reaction mechanism and kinetics of the reaction between HO and -C H O was performed at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311G(d,p) level of theory. Computational results show that the HO + -C H O reaction proceeds on both singlet and triplet potential energy surfaces (PESs). From an energetic point of view, the formation of C H O H and O triplet hydrogen abstraction is the most favorable channel while other product channels are negligible. In addition, the calculated rate constants for the title reaction over the temperature range of 238-398 K were calculated by the multiconformer transition state theory (MC-TST), and the calculated rate constants show a negative temperature dependence. The contributions of the other four reaction channels to the total rate constant are negligible.