Abstract
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.
| Original language | English |
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| Pages (from-to) | 7134-7139 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 12 |
| Issue number | 30 |
| DOIs | |
| State | Published - Aug 5 2021 |
Funding
We dedicate this paper to the memory of our colleague and collaborator, Prof. William L. Hase, who passed away during the preparation of this manuscript. Bill was a brilliant scientist, nurturing mentor, and generous friend. He will be deeply missed by the international physical chemistry community. We gratefully acknowledge financial support of this work by the National Natural Science Foundation of China (No. 21903004), the Teli Fellowship from Beijing Institute of Technology, China, the National Science Foundation of USA (CHE-1300886), and the Robert A. Welch Foundation of USA under Grant D-0005. Support is also provided by the High Performance Computing Center (HPCC) at Texas Tech University, under the direction of Alan Sill.