| Title | Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity |
| Author | |
| Corresponding Author | Li, 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 Type | Journal Article |
| Identifier | http://kc.sustech.edu.cn/handle/2SGJ60CL/490019 |
| Department | Department 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 Affilication | Department of Chemistry; Shenzhen Grubbs Institute; Southern University of Science and Technology |
| Corresponding Author Affilication | Department of Chemistry; Shenzhen Grubbs Institute; Southern University of Science and Technology; |
| First Author's First Affilication | Department 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).
|
| Files in This Item: | There are no files associated with this item. | |||||
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