title: Comprehensive theoretical studies on the reaction of 1-bromo-3,3,3-trifluoropropene with OH free radicals.
abstract: The potential energy surfaces (PES) for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals is probed theoretically at the CCSD/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. All the possible stationary and first-order saddle points along the reaction paths were verified by the vibrational analysis. The calculations account for all the product channels. Based on the calculated CCSD/aug-cc-pVDZ potential energy surface, the possible reaction mechanism is discussed. Six distinct reaction pathways of 1-bromo-3,3,3-trifluoropropene (BTP) with OH are investigated. The geometries, reaction enthalpies and energy barriers are determined. Canonical transition-state theory with Wigner tunneling correction was used to predict the rate constants for the temperature range of 290-3,000 K without any artificial adjustment, and the computed rate constants for elementary channels can be accurately fitted with three-parameter Arrhenius expressions. OH addition reaction channel and the H atom abstraction channels related to the carbon-carbon double bond are found to be the main reaction channels for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals while the products leading to CF3CHCH + BrOH and COHF2CHCBrH + F play a negligible role.
authors.affiliation: School of Biomedical Engineering, Tianjin Medical University, Tianjin 300070, China. zhml@mail.ustc.edu.cn
authors.forename: Meiling
authors.initials: M
authors.lastname: Zhang
authors.forename: Ce
authors.initials: C
authors.lastname: Song
authors.forename: Yan
authors.initials: Y
authors.lastname: Tian
mesh_terms: D002244:Carbon / Q000737:chemistry; D017402:Chlorofluorocarbons / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry*; D008956:Models, Chemical; D008962:Models, Theoretical; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics
chemical_list: D017402:Chlorofluorocarbons; D005609:Free Radicals; D017665:Hydroxyl Radical; D002244:Carbon; D006859:Hydrogen