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Prediction of the product channels in the reaction of the methyl radical with fulminic acid
Author(s) -
Nguyen Trong Nghia,
Nguyen Hue Minh Thi
Publication year - 2021
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21458
Subject(s) - chemistry , adduct , potential energy surface , reaction rate constant , atom (system on chip) , torr , molecule , kinetics , decomposition , computational chemistry , density functional theory , thermodynamics , organic chemistry , physics , quantum mechanics , computer science , embedded system
The reaction of CH 3 + HCNO was theoretically studied by both density functional theory and molecular orbital calculations and analyzed by quantum statistical methods. The potential energy surface was constructed at the UCCSD(T)//B3LYP/6‐311++G(3df,2p) + ZPE level. Four entrance channels are opened relating to the interaction of the CH 3 radical with each of the four atoms of the HCNO molecule, giving rise to 18 different product sets. The predicted geometries and heats of reaction are in good agreement with available experimental data. The major pathways involve addition of CH 3 to the C atom of HCNO with a small energy barrier of ∼4 kcal/mol forming both Z and E ‐HC(CH 3 )NO (IS1/IS1b) intermediates lying 45 or 44 kcal/mol, respectively, below the reactants. The nascent intermediates can collisionally be deactivated and subsequently decomposed into H + CH 3 CNO or isomerized prior to decomposition giving other products. Kinetics calculations covering the temperature range of 400‐2500 K, under pressures of 7.6 × 10 –1 to 7.6 × 10 5 Torr for N 2 , He, and Ar as the third bodies show that at 760 Torr N 2 , the adducts including both IS1 and IS1b are the major products at temperature below 600 K, whereas H + CH 3 CNO and CNO + CH 4 are the major products at T ≥ 1500 K. The total high‐pressure rate coefficient can well be expressed by the following three‐parameter equation: k ( T ) = 7.75 × 10 –16 T 1.69 exp (−1480 K/T) cm 3 molecule –1 s –1 .