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Direct dynamics study of the hydrogen abstraction reaction of CF 3 CH 2 Cl + Cl → CF 3 CHCl + HCl
Author(s) -
Zhao Yuan,
He Hongqing,
Zhang Jinglai,
Wang Li
Publication year - 2012
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.20709
Subject(s) - chemistry , hydrogen atom abstraction , reaction rate constant , ab initio , quantum tunnelling , transition state theory , density functional theory , atmospheric temperature range , range (aeronautics) , thermodynamics , hydrogen , potential energy surface , atomic physics , computational chemistry , quantum mechanics , physics , kinetics , organic chemistry , materials science , composite material
Abstract The hydrogen abstraction reaction of Cl atoms with CF 3 CH 2 Cl (HCFC‐133a) is investigated by using density function theory and ab initio approach, and the rate constants are calculated by using the dual‐level direct dynamics method. Optimized geometries and frequencies of reactants, transition state, and products are computed at the B3LYP/6‐311+G(2d,2p) level. To refine the energetic information along the minimum energy path, single‐point energy calculations are carried out at the G3(MP2) level of theory. The interpolated single‐point energy method is employed to correct the energy profiles for the title reaction. The rate constants are evaluated by using the canonical variational transition state theory with a small‐curvature tunneling correction over a wide range of temperature, 200–2000 K. The variational effect for the reaction is moderate at low temperatures and very small at high temperatures. However, the tunneling correction has an important contribution in the lower temperature range. The agreement between calculated rate constants and available experimental values is good at lower temperatures but diverges significantly at higher temperatures. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 661–667, 2012