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DOI | 10.1038/s41467-019-12138-0 |
Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism | |
Zhao, Zhiqiang1,2; Zhang, Zhaojun1; Liu, Shu1; Zhang, Dong H.1,3,4 | |
2019-09-11 | |
发表期刊 | NATURE COMMUNICATIONS
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ISSN | 2041-1723 |
出版年 | 2017 |
卷号 | 8 |
文章类型 | Article |
语种 | 英语 |
国家 | Peoples R China |
英文摘要 | Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode. |
领域 | 资源环境 |
收录类别 | SCI-E |
WOS记录号 | WOS:000394525100001 |
WOS关键词 | GAS-PHASE REACTIONS ; S(N)2 NUCLEOPHILIC-SUBSTITUTION ; QUANTUM DYNAMICS ; TRANSLATIONAL ACTIVATION ; SN2 REACTION ; TEMPERATURE-DEPENDENCE ; ENERGY ; KINETICS ; SOLVENT ; ATOM |
WOS类目 | Multidisciplinary Sciences |
WOS研究方向 | Science & Technology - Other Topics |
URL | 查看原文 |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/204533 |
专题 | 资源环境科学 |
作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China; 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China; 3.Univ Sci & Technol China, Ctr Adv Chem Phys, Hefei 230026, Peoples R China; 4.Univ Sci & Technol China, Frontier Ctr Quantum Sci & Technol 2011, Hefei 230026, Peoples R China |
推荐引用方式 GB/T 7714 | Zhao, Zhiqiang,Zhang, Zhaojun,Liu, Shu,et al. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism[J]. NATURE COMMUNICATIONS,2019,8. |
APA | Zhao, Zhiqiang,Zhang, Zhaojun,Liu, Shu,&Zhang, Dong H..(2019).Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism.NATURE COMMUNICATIONS,8. |
MLA | Zhao, Zhiqiang,et al."Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism".NATURE COMMUNICATIONS 8(2019). |
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