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Quantum chemical study of gas-phase reactions of isoprene with OH radicals producing highly oxidised second-generation products

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Abstract

The formation of secondary organic aerosols caused by atmospheric oxidation of isoprene is harmful to human health and the climate; thus, isoprene oxidation is further mandatory to obtain less harmful or harmless highly oxidised products. In this numerical investigation, 2-hydroperoxy-2-methylbut-3-en-1-ol (ISOPOOH) was considered the model compound to investigate the formation of three RO2 radicals (C5H11O4, C5H11O6 and C5H11O5) and two saturated highly oxidised products (C5H12O6 and C5H10O6). The complete reaction network and its thermodynamics and kinetics were analysed to obtain the most probable and feasible reaction pathways. Four different levels of theories (HF, B3LYP, M06-2X and ωB97XD with basis set of 6-31+g(d,p)) were employed to explore a global minimum of ISOPOOH. All theories provided approximately close energetics; however, because of the novelty of the functional and parameterisation of the basis set, the ωB97XD functional was selected to examine the reaction mechanism. C5H12O6 was formed as the second-generation highly oxidised product during ISOPOOH oxidation.

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  1. Department of Physics and Material Science (formerly known as Department of Applied Science), Madan Mohan Malaviya University of Technology, Gorakhpur, U.P., 273010, India

    Anand Mohan Verma & Satya Pal Singh

  2. Department of Physics, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur, U.P., 273009, India

    R. P. Ojha

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  1. Anand Mohan Verma
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  2. Satya Pal Singh
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Verma, A.M., Singh, S.P. & Ojha, R.P. Quantum chemical study of gas-phase reactions of isoprene with OH radicals producing highly oxidised second-generation products. J Mol Model 27, 62 (2021). https://doi.org/10.1007/s00894-021-04666-8

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