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

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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.

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Funding

Project supported: Fundamental Research Funds for the Central Universities (31920220063), the National Natural Science Foundation of China (21968032, 22165025, and 22262031), Chemistry Discipline Innovation Team of Northwest Minzu University (1110130139 and 1110130141).

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Authors and Affiliations

  1. Key Laboratory of Environment-Friendly Composite Materials of the State Ethnic Affairs Commission, Key Laboratory for Utility of Environment-Friendly Composite Materials and Biomass in University of Gansu Province, College of Chemical Engineering, Gansu Provincial Biomass Function Composites Engineering Research Center, Northwest Minzu University, Gansu, 730030, Lanzhou, China

    Zhang Fupeng, Liang Junxi, Qi Bomiao, Lu Mengmeng, Pang Shaofeng, Wang Yanbin & Su Qiong

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  1. Zhang Fupeng
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  2. Liang Junxi
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  3. Qi Bomiao
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  4. Lu Mengmeng
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  5. Pang Shaofeng
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  6. Wang Yanbin
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  7. Su Qiong
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Contributions

Liang Junxi: conceptualization, methodology, and funding acquisition. Zhang Fupeng: validation, formal analysis, and writing original draft. Qi Bomiao: visualization. Lu Mengmeng: funding acquisition and project administration. Pang Shaofeng: data curation. Wang Yanbin: writing review and editing. Su Qiong: project administration.

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Correspondence to Liang Junxi or Su Qiong.

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Fupeng, Z., Junxi, L., Bomiao, Q. et al. A comparable DFT study on reaction of CHCl•− with O3 and S2O. J Mol Model 29, 85 (2023). https://doi.org/10.1007/s00894-023-05483-x

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