Micro-dynamics of Hydrogen Abstraction Reaction Between CH4-nFn(n=1—3) and CH3

Chem. J. Chinese Universities

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Micro-dynamics of Hydrogen Abstraction Reaction Between CH_4-nF_n(n=1—3) and CH₃

FENG Li-Xia¹, WANG Wen-Liang¹, LI Lin¹, WANG Wei-Na¹, LUO Qiong^1,2, LI Qian-Shu^1,2

1. School of Chemistry and Materials Science, Shaanxi Normal University, Xi'an 710062, China;
2. School of Science, Beijing Institute of Technology, Beijing 100081, China

Received:2005-08-25 Revised:1900-01-01 Online:2006-09-10 Published:2006-09-10
Contact: WANG Wen-Liang

Abstract

Abstract: QCISD(T)/6-311+G(d,p)//BHandHLYP/6-311G(d,p) method was employed to reveal the reaction mechanism and to predict the micro-kinetic character of the hydrogen abstraction reactions of H_4-nF_n(n=1~3) with CH₃. The rate constants of the reactions were evaluated by means of the canonical variational transition-state theory(CVT) conjunction with small-curvature tunneling(SCT) correction in the temperature range of 200—3 000 K. In this study, the reaction energies ΔE of R1a, R2a and R3 are -12.7, -9.5 and 11.8 kJ/mol, the potential barriers ΔE^≠were 67.0, 62.2 and 67.5 kJ/mol, respectively. At 437 K, the CVT/SCT rate constants were 6.72×10^-19, 8.01×10^-18and 8.82×10^-20 cm³/(molecule·s), which were in agreement with the experimental values 3.31×10^-19, 1.05×10^-18 and 8.33×10^-20 cm³/(molecule·s). The results indicate that the tunneling effect was considerable at the lower temperatures, while the variational effect was almost negligible in the entire process.

Key words: H4-nFn(n=1~3), H-abstraction reaction, QCISD(T)//BHandHLYP, Rate constant

CLC Number:

O641

TrendMD:

FENG Li-Xia¹, WANG Wen-Liang¹, LI Lin¹, WANG Wei-Na¹, LUO Qiong^1,2, LI Qian-Shu^1,2
. Micro-dynamics of Hydrogen Abstraction Reaction Between CH_4-nF_n(n=1—3) and CH₃
[J]. Chem. J. Chinese Universities, doi: .

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Micro-dynamics of Hydrogen Abstraction Reaction Between CH_4-nF_n(n=1—3) and CH₃

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