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Quantum chemical study of the reaction of trichloroethylene with O( 3 P)
Author(s) -
Messaoudi Boulanouar
Publication year - 2020
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.21372
Subject(s) - chemistry , hydrogen atom abstraction , reaction rate constant , quantum chemical , atom (system on chip) , hydrogen atom , trichloroethylene , computational chemistry , photochemistry , hydrogen , molecule , kinetics , organic chemistry , group (periodic table) , physics , quantum mechanics , computer science , embedded system
The adiabatic mechanism of the reaction of trichloroethylene with O( 3 P), exploring the various O‐atom addition and H‐atom abstraction channels, is theoretically studied at the MP2/6‐311++G(2d, 2p), MP2/aug‐cc‐pVTZ, CCSD/6‐31G(d), G3, and CBS‐QB3 levels of theory. From a kinetic point of view, the addition to the less substituted carbon atom of the double bond is more favorable than the addition to the more substituted carbon. Such O‐atom addition reactions are favored over the one possible hydrogen‐abstraction reaction. Calculations of the present study showed that five products are obtained: HCCl + C(O)Cl 2 (P1), Cl + ClC(O)CHCl (P2), H + ClC(O)CCl 2 (P3), Cl + HC(O)CCl 2 (P4), and CH(O)Cl + CCl 2 (P5). The products P2 and P4 are found to be the most favored ones. The kinetic calculations of rate constant in the range of 285–395 K are performed at the CBS‐QB3 level of theory and are in conformity with the experimental outcomes.