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. 2023 Mar 3;29(4):85.
doi: 10.1007/s00894-023-05483-x.

A comparable DFT study on reaction of CHCl•- with O3 and S2O

Zhang Fupeng  1 , Liang Junxi  2 , Qi Bomiao  1 , Lu Mengmeng  1 , Pang Shaofeng  1 , Wang Yanbin  1 , Su Qiong  3
Affiliations

A comparable DFT study on reaction of CHCl•- with O3 and S2O

Zhang Fupeng et al. J Mol Model. .

Abstract

Context: In this discussion, we began building two model, S2O + CHCl•- and O3 + CHCl•-, using DFT-BHandHLYP method, to study their reactions mechanisms on singlet PES. For this purpose, we hope to explore the effects of the difference between sulfur and oxygen atoms on the CHCl•- anion. Experimentalists and computer scientists may utilize the collected data to generate a wide range of hypotheses for experimental phenomena and predictions, allowing them to realize their full potential.

Methods: The ion-molecule reaction mechanism of CHCl•- with S2O and O3 was studied using the DFT-BHandHLYP level of theory with the aug-cc-pVDZ basis set. Our theoretical findings show that Path 6 is the favored reaction pathway for CHCl•- + O3 reaction as identified by the O-abstraction reaction pattern. Comparing to the direct H- and Cl-abstraction mechanisms, the reaction (CHCl•- + S2O) prefers the intramolecular SN2 reaction pattern. Moreover, the calculated results demonstrated that the CHCl•- + S2O reaction is thermodynamically more favorable than the CHCl•- + O3 reaction, which is kinetically more advantageous. As a result, if the required reaction condition in the atmospheric process is met, the O3 reaction will happen more effectively. In terms of kinetics and thermodynamics viewpoints, the CHCl•- anion was very effective in eliminating S2O and O3.

Keywords: Carbene radical anion; Mechanism; Quantum chemical calculation.

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