中文版 | English
Title

Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity

Author
Corresponding AuthorLi, Xin; Chung, Lung Wa
Publication Years
2023
DOI
Source Title
ISSN
1948-7185
Abstract
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.
URL[Source Record]
Indexed By
Language
English
Important Publications
NI Journal Papers
SUSTech Authorship
First ; Corresponding
Funding Project
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 Research Area
Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics
WOS Subject
Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical
WOS Accession No
WOS:000932503800001
Publisher
Data Source
Web of Science
Citation statistics
Cited Times [WOS]:0
Document TypeJournal Article
Identifierhttp://kc.sustech.edu.cn/handle/2SGJ60CL/490019
DepartmentDepartment of Chemistry
深圳格拉布斯研究院
Affiliation
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
First Author AffilicationDepartment of Chemistry;  Shenzhen Grubbs Institute;  Southern University of Science and Technology
Corresponding Author AffilicationDepartment of Chemistry;  Shenzhen Grubbs Institute;  Southern University of Science and Technology;  
First Author's First AffilicationDepartment of Chemistry;  Shenzhen Grubbs Institute
Recommended Citation
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.
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.
MLA
Ma, Zhifeng,et al."Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity".Journal of Physical Chemistry Letters (2023).
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