| Autor: |
Chongyang Zhao, Ditte L. Thomsen, Jing Xie, Xinyou Ma, Xiangyu Wu, Veronica M. Bierbaum |
| Rok vydání: |
2021 |
| Předmět: |
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| Zdroj: |
The Journal of Physical Chemistry Letters. 12:7134-7139 |
| ISSN: |
1948-7185 |
| Popis: |
Direct dynamics simulation of singly hydrated peroxide ion reacting with CH3Cl reveals a new product channel that forms CH3OH + Cl- + HOOH, besides the traditional channel that forms CH3OOH + Cl- + H2O. This finding shows that singly hydrated peroxide ion behaves as a dual nucleophile through proton transfer between HOO-(H2O) and HO-(HOOH). Trajectory analysis attributes the occurrence of the thermodynamically and kinetically unfavored HO--induced pathway to the entrance channel dynamics, where extensive proton transfer occurs within the deep well of the prereaction complex. This study represents the first example of a single solvent molecule altering the nucleophile in a gas-phase ion-molecule nucleophilic substitution reaction, in addition to reducing the reactivity and affecting the dynamics, signifying the importance of dynamical effects of solvent molecules. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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