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A comprehensive quantum chemical study on the mechanism and kinetics of atmospheric reactions of 3-chloro-2-methyl-1-propene with OH radical

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Abstract

The detailed reaction mechanism of 3-chloro-2-methyl-1-propene (3CMP) with OH radical was investigated by employing highly accurate electronic structure calculations and kinetic modelling. Due to the unsaturated structure of 3CMP, it is highly reactive in the troposphere with OH radical. The fate of the so-formed alkyl radical intermediates and intermediate adducts in the favourable pathways is determined by its reaction with other atmospheric oxidants, such as HO2, NO and NO2 radicals. The rate constants computed within the temperature range of 200–1000 K for the favourable hydrogen atom abstraction and OH radical addition reactions are in reasonable agreement with the available experimental values. The oxidation of 3CMP results in the formation of stable chlorinated products, such as chloroacetone and formyl chloride, which are identified experimentally. These products may be transported to the stratosphere which will affect the ozone layer.

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Acknowledgements

The authors are thankful to UGC and Department of Science and Technology (DST), India, for funding to establish the high-performance computing facility under the SAP and PURSE programs.

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Authors and Affiliations

  1. Department of Physics, Vellalar College for Women, Erode, 638 012, India

    R. Bhuvaneswari

  2. Department of Physics, Bharathiar University, Coimbatore, 641 046, India

    R. Bhuvaneswari & K. Senthilkumar

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  1. R. Bhuvaneswari
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  2. K. Senthilkumar
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Correspondence to K. Senthilkumar.

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214_2019_2518_MOESM1_ESM.doc

The TST, CVT, TST (SCT) and CVT (SCT) rate constants (cm3 molecule−1 s−1) for the initial H-abstraction reactions (R2 and R3) and OH-addition reactions (R4 and R5) of 3CMP with OH radical are given in Table S1. Relative energy, ΔETot (kcal/mol), enthalpy, ΔH298 (kcal/mol), and Gibbs free energy, ΔG298 (kcal/mol), for the reactions of radical intermediates, I2, I3, 45 and I5, calculated at M06-2X, ωB97XD and CCSD(T) level of theories are summarized in Table S2, S3, S4 and S5. (DOC 1109 kb)

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Bhuvaneswari, R., Senthilkumar, K. A comprehensive quantum chemical study on the mechanism and kinetics of atmospheric reactions of 3-chloro-2-methyl-1-propene with OH radical. Theor Chem Acc 139, 2 (2020). https://doi.org/10.1007/s00214-019-2518-y

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  • DOI: https://doi.org/10.1007/s00214-019-2518-y

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