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Theoretical study and rate constants calculation for the reactions X + CF 3 CH 2 OCF 3 (X = F, Cl, Br)
Author(s) -
Zhang Hui,
Liu Yang,
Liu JingYao,
Li ZeSheng
Publication year - 2011
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.22897
Subject(s) - chemistry , hydrogen atom abstraction , transition state theory , reaction rate constant , atmospheric temperature range , curvature , quantum tunnelling , thermodynamics , atomic physics , computational chemistry , hydrogen , physics , mathematics , geometry , quantum mechanics , kinetics , organic chemistry
The multiple‐channel reactions X + CF 3 CH 2 OCF 3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6‐31+G(d,p) level, and energetic information is further refined by the MC‐QCISD (single‐point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small‐curvature tunneling (SCT) correction over the temperature range 200–2000 K. The theoretical three‐parameter expressions for the three channels k 1a ( T ) = 1.24 × 10 −15 T 1.24 exp(−304.81/ T ), k 2a ( T ) = 7.27 × 10 −15 T 0.37 exp(−630.69/ T ), and k 3a ( T ) = 2.84 × 10 −19 T 2.51 exp(−2725.17/ T ) cm 3 molecule −1 s −1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2012