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RESEARCH ARTICLE
Contents Vol 65(2)

Dual-Level Direct Dynamics Studies on the Hydrogen Abstraction Reactions of CH2CH3–n Xn + HBr (X = Cl, Br and n = 1, 2)

Li Wang A , Jianxiang Zhao A , Hongqing He B and Jinglai Zhang A C
+ Author Affiliations
- Author Affiliations

A Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China.

B Wuhan Center for Magnetic Resonance, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China.

C Corresponding author. Email: zhangjinglai@henu.edu.cn

Australian Journal of Chemistry 65(2) 160-168 https://doi.org/10.1071/CH11420
Submitted: 27 October 2011  Accepted: 21 December 2011   Published: 1 February 2012

Abstract

The reactions of the HBr molecule with CH2CH2Cl (reaction R1), CH2CHCl2 (R2), CH2CH2Br (R3) and CH2CHBr2 (R4) are investigated by a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points were calculated at the MPW1K/6–311+G(d,p) and BMK/6–311+G(d,p) levels. To refine the reaction enthalpy and energy barrier height of each reaction, single-point energy calculations were carried out by the G2M(RCC5) method based on the geometries optimized at the above-mentioned two levels. Using the canonical variational transition state theory or the canonical variational transition state theory with the small-curvature tunneling correction, the rate constants of HBr with CH2CH2Cl (R1), CH2CHCl2 (R2), CH2CH2Br (R3), and CH2CHBr2 (R4) were calculated over a wide temperature range of 200–2000 K at the G2M(RCC5)//MPW1K/6–311+G(d,p) level. The effect of chlorine or bromine substitution on the ethyl radical reactivity is discussed. Finally, the total rate constants are fitted by two models, i.e. three-parameter and four-parameter expressions.


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