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Dual‐level direct dynamics studies on the reaction Cl + CHBr 2 Cl
Author(s) -
Zhang Hui,
Wu JiaYan,
Li ZeSheng,
Liu JingYao,
Sheng Li,
Sun ChiaChung
Publication year - 2005
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20283
Subject(s) - chemistry , reaction rate constant , abstraction , atmospheric temperature range , quantum tunnelling , computational chemistry , transition state theory , atomic physics , thermodynamics , physics , kinetics , quantum mechanics , philosophy , epistemology
Theoretical investigations are carried out on the multichannel reaction CHBr 2 Cl + Cl by means of direct dynamics methods. The minimum energy path (MEP) is obtained at the BH&H‐LYP/6‐311G(d,p) level, and energetic information is further refined at the CCSD(T)/6‐311+G(2df,2p) (single‐point) level. The rate constants for three reaction channels, H‐abstraction, Br‐abstraction, and Cl‐abstraction, are calculated by using the improved canonical variational transition state theory (ICVT) incorporating with the small‐curvature tunneling (SCT) correction. The theoretical overall rate constants are in good agreement with the available experimental data and are found to be k = 2.58 × 10 −15 T 1.18 exp(−861.17/ T ) cm 3 molecule −1 s −1 over the temperature range 200–2400 K. For the title reaction, H‐abstraction reaction channel is the major channel at the lower temperatures, while as the temperature increases, the contribution of Br‐abstraction reaction channel should be taken into account. At 2180 K, the rate constants of these two pathways are equal. Cl‐abstraction reaction channel is minor channel over the whole temperature region. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1421–1426, 2005