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Computational studies on the mechanism and kinetics of Cl reaction with C 2 H 5 I
Author(s) -
Jia XiuJuan,
Liu YouJun,
Sun JingYu,
Sun Hao,
Wang Fang,
Su ZhongMin,
Pan XiuMei,
Wang RongShun
Publication year - 2010
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.21516
Subject(s) - arrhenius equation , kinetics , chemistry , kinetic isotope effect , quantum tunnelling , reaction rate constant , atmospheric temperature range , chemical kinetics , deuterium , thermodynamics , hydrogen atom abstraction , hydrogen , range (aeronautics) , displacement (psychology) , kinetic energy , atomic physics , activation energy , physics , materials science , quantum mechanics , organic chemistry , psychology , composite material , psychotherapist
The dual‐level direct kinetics method has been used to investigate the multichannel reactions of C 2 H 5 I + Cl. Three hydrogen abstraction channels and one displacement process are found for the title reaction. The calculation indicates that the hydrogen abstraction from CH 2 group is the dominant reaction channel, and the displacement process may be negligible because of the high barrier. The rate constants for individual reaction channels are calculated by the improved canonical variational transition‐state theory with small‐curvature tunneling correction over the temperature range of 220–1500 K. Our results show that the tunneling correction plays an important role in the rate constant calculation in the low‐temperature range. Agreement between the calculated and experimental data available is good. The Arrhenius expression k ( T ) = 2.33 × 10 −16 T 1.83 exp(−185.01/ T ) over a wide temperature range is obtained. Furthermore, the kinetic isotope effects for the reaction C 2 H 5 I + Cl are estimated so as to provide theoretical estimation for future laboratory investigation. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010