Kinetics of hydrogen abstraction and addition reactions of 3-hexene by OH radicals (PDF)
发布时间：2025-04-30
点击次数：
- 发布时间：
- 2025-04-30
- 论文名称：
- Kinetics of hydrogen abstraction and addition reactions of 3-hexene by OH radicals (PDF)
- 发表刊物：
- J Phys Chem
- 摘要：
- Rate coefficients of H-atom abstraction and H-atom addition reactions of 3-hexene by the hydroxyl radicals were determined using both conventional transition-state theory and canonical variational transition-state theory, with potential energy surface (PES) evaluated at the CCSD(T)/CBS//BHandHLYP/6-311G (d, p) level and quantum mechanical effect corrected by the compounded methods including one-dimensional Wigner method, multi-dimensional zero-curvature tunneling method and small-curvature tunneling method. Results reveal that accounting for approximate 70% of the overall H-atom abstractions occur in the allylic site via both direct and indirect channels. The indirect channel containing two Van der Waals pre-reactive complexes exhibits two times larger rate coefficient relative to the direct one. The OH-addition reaction also contains two Van der Waals complexes, and its submerged barrier results in a negative temperature coefficient behavior at low temperatures. In contrast, The OH-addition pathway dominates only at temperatures below 450 K whereas the H-atom abstraction reactions dominate overwhelmingly at temperature over 1000 K. All of the rate coefficients calculated with an uncertainty of a factor of 5 were fitted in a quasi-Arrhenius formula. Analyses on the PES, minimum reaction path and activation free Gibbs energy were also performed in this study.
- 合写作者：
- Yang FY, Deng FQ, Pan YS, Zhang YJ, Tang CL, Huang ZH
- 卷号：
- 2017, 121(9): 1877-1889
- 页面范围：
- 1877-1889
- 是否译文：
- 否
- 发表时间：
- 2017-02-15