Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

doi:10.1038/ncomms14506

	Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism
	Zhao, Zhiqiang 1,2; Zhang, Zhaojun 1; Liu, Shu 1; Zhang, Dong H.1,3,4
刊名	NATURE COMMUNICATIONS
	2017-02-22
卷号	8
ISSN号	2041-1723
DOI	10.1038/ncomms14506
文献子类	Article
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.
WOS关键词	S(N)2 NUCLEOPHILIC-SUBSTITUTION ; POTENTIAL-ENERGY SURFACE ; GAS-PHASE REACTIONS ; QUANTUM DYNAMICS ; TRANSLATIONAL ACTIVATION ; SN2 REACTION ; TEMPERATURE-DEPENDENCE ; CARBON-ATOM ; KINETICS ; SOLVENT
WOS研究方向	Science & Technology - Other Topics
语种	英语
出版者	NATURE PUBLISHING GROUP
WOS记录号	WOS:000394525100001
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/169660]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Liu, Shu; Zhang, Dong H.
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,2017,8.
APA	Zhao, Zhiqiang,Zhang, Zhaojun,Liu, Shu,&Zhang, Dong H..(2017).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(2017).