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Theoretical investigations on mechanisms and pathways of CH2ClO2/CHCl2O2 with ClO reactions in the atmosphere

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Abstract

A global and systematic theoretical research on the singlet and triplet potential energy surfaces (PESs) of the CH2ClO2/CHCl2O2 with ClO reactions are done at the CCSD(T)//B3LYP level and accompanied with RRKM computations to forecast the mechanism and distribution of products. The simulation results revealed that, on the singlet PES, products P1 (CHClO + HO2 + Cl)/P1 (CCl2O + HO2 + Cl) from IM1 (CH2ClOOOCl)/IM1 (CHCl2OOOCl) are forecasted to the primary products of the CH2ClO2/CHCl2O2 + ClO reactions, which are initiated by the oxygen atom of ClO radical addition to the terminal-O atom of CH2ClO2/CHCl2O2 barrierlessly, while other product channels contribute less to the whole reactions owing to higher barriers. Two other isomers, including IM2 (CH2ClOOClO) and IM3 (CH2ClOClO2) for the CH2ClO2 + ClO reaction, and three other isomers, including IM2 (CHCl2OOClO), IM3 (CHCl2OClO2), and IM4 (CHCl2ClO3) for the CHCl2O2 + ClO reaction, could be produced as less significant products. RRKM calculations presented that the initial adducts IM1 (CH2ClOOOCl)/IM1 (CHCl2OOOCl) are the primary products at T < 400 K and T < 600 K, respectively, and products P1 (CHClO + HO2 + Cl)/P1 (CCl2O + HO2 + Cl) are dominant the reactions at T ≥ 400 K and T ≥ 600 K, respectively. The atmospheric lifetime of CH2ClO2 and CHCl2O2 in ClO is around 4.61 and 3.24 h, respectively.

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Funding

This work was financially supported by the Natural Science Foundations of China (No. 21707062) and the Scientific Research Starting Foundation of Mianyang Normal University (No. QD2016A007).

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Authors and Affiliations

  1. Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People’s Republic of China

    Yunju Zhang, Yuxi Sun, Baomei Huang, Zhiguo Wang & Yan Zhou

  2. College of Chemistry and Life Science, Institute of functional molecules, Chengdu Normal University, Chengdu, 611130, Sichuan, People’s Republic of China

    Bing He

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  1. Yunju Zhang
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Correspondence to Yunju Zhang.

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Zhang, Y., He, B., Sun, Y. et al. Theoretical investigations on mechanisms and pathways of CH2ClO2/CHCl2O2 with ClO reactions in the atmosphere. Environ Sci Pollut Res 27, 20457–20468 (2020). https://doi.org/10.1007/s11356-020-08315-0

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