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Theoretical study on HO 2 ‐initiated atmospheric oxidation of halogenated carbonyls
Author(s) -
Long Bo,
Long ZhengWen,
Wang YiBo,
Zhang WeiJun,
Long ChaoYun,
Qin ShuiJie
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23189
Subject(s) - chemistry , oxalyl chloride , bromide , density functional theory , reaction rate constant , transition state , quantum chemical , medicinal chemistry , chloride , computational chemistry , reaction mechanism , transition state theory , photochemistry , inorganic chemistry , kinetics , molecule , catalysis , organic chemistry , physics , quantum mechanics
Abstract The initial reactions of HO 2 with oxalyl dichloride, oxalyl dibromide, acetyl chloride, and acetyl bromide are studied for the first time using the density functional theory with CAM‐B3LYP and wB97XD, CBS‐QB3, and G3 theoretical methods and the transition state theory. The reactions occur via the similar mechanism that the prereactive complex is formed before the transition state and product. The calculated results demonstrate that the HO 2 radical with ClC(O)C(O)Cl and BrC(O)C(O)Br reactions is feasible and could play a significant role in the atmosphere because the barriers are 0.13 kcal/mol, −0.05 kcal/mol with respect to the free reactants, respectively at the CBS‐QB3 level of theory. In addition, the rate constants of the HO 2 + ClC(O)C(O)Cl and HO 2 + BrC(O)C(O)Br reactions are computed to be 1.37 × 10 −15 cm 3 mol −1 s −1 , 1.70 × 10 −15 cm 3 mol −1 s −1 at 298 K. However, the HO 2 reactions with acetyl chloride and acetyl bromide are of no importance because of higher activated barrier and slower rate constant. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011