南方科技大学知识苑(SUSTech KC): Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity

题名	Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity
作者	Ma, Zhifeng1,2 ; Yan, Zeyin1,2 ; Li, Xin1,2 ; Chung, Lung Wa1,2
通讯作者	Li, Xin; Chung, Lung Wa
发表日期	2023
DOI	10.1021/acs.jpclett.2c03461
发表期刊	Journal of Physical Chemistry Letters 影响因子和分区
ISSN	1948-7185
卷号	14 期号:5页码:1124-1132
摘要	Quantum tunneling and external electric fields (EEFs) can promote some reactions. However, the synergetic effect of an EEF on a tunneling-involving reaction and its temperature-dependence is not very clear. In this study, we extensively investigated how EEFs affect three reactions that involve hydrogen-or (ground-and excited-state) carbon-tunneling using reliable DFT, DLPNO-CCSD(T1), and variational transition-state theory methods. Our study revealed that oriented EEFs can significantly reduce the barrier and corresponding barrier width (and vice versa) through more electrostatic stabilization in transition states. These EEF effects enhance the nontunneling and tunneling-involving rates. Such EEF effects also decrease the crossover temperatures and quantum tunneling contribution, albeit with lower and thinner barriers. Moreover, EEFs can modulate and switch on/off the tunneling driven 1,2-H migration of hydroxycarbenes under cryogenic conditions. Furthermore, our study predicts for the first time that EEF/tunneling synergy can control the chemo-or site selectivity of one molecule bearing two similar/same reactive sites.
相关链接	[来源记录]
收录类别	SCI ; EI
语种	英语
重要成果	NI论文
学校署名	第一 ; 通讯
资助项目	National Natural Science Foundation of China["21873043","21933003","22193020","22193023"] ; Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:000932503800001
出版者	AMER CHEMICAL SOC
EI入藏号	20230513536397
EI主题词	Electric fields ; Electron tunneling ; Electronic states ; Temperature distribution
EI分类号	Thermodynamics:641.1 ; Electricity: Basic Concepts and Phenomena:701.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Electronic Structure of Solids:933.3
来源库	Web of Science
引用统计	被引频次[WOS]：4
成果类型	期刊论文
条目标识符	http://sustech.caswiz.com/handle/2SGJ60CL/490019
专题	理学院_化学系深圳格拉布斯研究院
作者单位	1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518055, Peoples R China 2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
第一作者单位	化学系; 深圳格拉布斯研究院; 南方科技大学
通讯作者单位	化学系; 深圳格拉布斯研究院; 南方科技大学
第一作者的第一单位	化学系; 深圳格拉布斯研究院
推荐引用方式 GB/T 7714	Ma, Zhifeng,Yan, Zeyin,Li, Xin,et al. Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity[J]. Journal of Physical Chemistry Letters,2023,14(5):1124-1132.
APA	Ma, Zhifeng,Yan, Zeyin,Li, Xin,&Chung, Lung Wa.(2023).Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity.Journal of Physical Chemistry Letters,14(5),1124-1132.
MLA	Ma, Zhifeng,et al."Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity".Journal of Physical Chemistry Letters 14.5(2023):1124-1132.