Theoretical kinetics of hydrogen abstraction and addition reactions of 3-hexene by H, Ö(3P) and ĊH3 (PDF)
发布时间：2025-04-30
点击次数：
- 发布时间：
- 2025-04-30
- 论文名称：
- Theoretical kinetics of hydrogen abstraction and addition reactions of 3-hexene by H, Ö(3P) and ĊH3 (PDF)
- 发表刊物：
- Combust Flame
- 摘要：
- H-atom abstraction and addition are the two most important reactions in alkene oxidation. As a complement of our synchronization work of 3-hexene chemistry (Feiyu Yang et al., Kinetics of Hydrogen Abstraction and Addition Reactions of 3-Hexene by ȮH Radicals, J. Phys. Chem. A 2017, 121, 1877–1889), high-accuracy electronic structure calculations (DLPNOCCSD(T)/CBS) and canonical variational transition state theory are used to predict the rate coefficients of the H-atom abstraction and addition reactions of 3-hexene + ĊH3/Ḣ/Ö system. Although ĊH3/Ḣ/Ö are all nonpolar radicals, Ḣ + 3-hexene system shows some unique features. Unlike the 3-hexene + ĊH3/Ö systems, the potential energy surface of 3-hexene + Ḣ system exhibits a unique “negative well” characteristic, suggesting the energy of the well is higher than its corresponding reactant or product. Analysis shows that the “negative well” characteristic is caused by the relative larger zero-point energies of Van der Waals complex of H + 3-hexene system. Moreover, the evolution of adiabatic ground-state energy shows wells/well-like curves at both reactant and product sides for 3-hexene + ĊH3 and Ö systems, but only at reactant end for 3-hexene + Ḣ system. Vibrational analysis reveals that for 3-hexene + ĊH3 and Ö systems, the wells/well-like curves are generated by the C = C double bond stretch motion, while it is generated by the forming HH single bond stretch motion for 3-hexene + Ḣ system. Branching ratio shows that addition and abstraction dominate at low and high temperatures and the critical temperatures are 478 K, 794 K and 735 K for 3-hexene + ĊH3, Ḣ and Ö systems, respectively. Rate coefficients with a conservative uncertainty of a factor of 5 are estimated based on similar algorithm of Sun and Law. In addition, analyses on the potential energy surface, minimum energy path, adiabatic ground-state energy and activation free Gibbs energy change are also performed in this work.
- 合写作者：
- Yang FY, Zhang YJ, Sun WC, Zhao Q, Huang WL, Qin XK, Huang ZH
- 卷号：
- 2018, 197: 449-462
- 页面范围：
- 449-462
- 是否译文：
- 否
- 发表时间：
- 2018-11-15
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