Theoretical Studies on the CH3CH2S Radical Hydrogen Shift Isomerization and Dissociation Reaction

Chem. J. Chinese Universities

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Theoretical Studies on the CH₃CH₂S Radical Hydrogen Shift Isomerization and Dissociation Reaction

SHI Zhao-Hui¹, WANG Wen-Liang¹*, WANG Wei-Na¹, LI Chun-Ying², LÜ Jian²

1. Key Laboratory for Macromolecular Science of Shanxi Province, School of Chemistry and Materials Science, Shanxi Normal University, Xi’an 710062, China;
2. Xi’an Modern Chemistry Research Institute, Xi’an 710065, China

Received:2007-02-05 Revised:1900-01-01 Online:2008-04-10 Published:2008-04-10
Contact: WANG Wen-Liang

Abstract

Abstract: Density functional theory B3LYP/6-311+G(d,p) method was employed to reveal the micro-kine-tic character of the hydrogen shift isomerization and dissociation reaction of the CH₃CH₂S. In order to obtain more reliable energies, the single point calculations were carried out at the QCISD(T)/6-311++G(d,p) level of theory. 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 over a wide range of temperature 200—2000 K at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311+G(d,p) level. In this study, the potential barriers ΔE^≠ of the 1,2-H shift, 1,3-H shift, C—C dissociation and β-C—H dissociation reactions of the CH₃CH₂S radical are 149.74, 144.34, 168.79 and 198.29 kJ/mol, respectively. The 1,2-H shift is the major reaction process when temperature is lower than 800 K, and C—C dissociation reaction became the dominant when temperature is higher than 1800 K, and 1,3-H shift is the major pathway when temperature is between 1300 and 1800 K. The β-C—H dissociaton reacton always play a minor role over the whole temperature region.

Key words: CH₃CH₂S, Isomerization reaction, Dissociation reaction, Rate constant

CLC Number:

O641

TrendMD:

SHI Zhao-Hui¹, WANG Wen-Liang¹*, WANG Wei-Na¹, LI Chun-Ying², LÜ Jian². Theoretical Studies on the CH₃CH₂S Radical Hydrogen Shift Isomerization and Dissociation Reaction[J]. Chem. J. Chinese Universities, doi: .

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Theoretical Studies on the CH₃CH₂S Radical Hydrogen Shift Isomerization and Dissociation Reaction

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