Acta Chimica Sinica ›› 2008, Vol. 66 ›› Issue (5): 497-504.     Next Articles

Original Articles

噻吩光解反应机理的理论研究

张文雨,丁万见*,刘若庄*   

  1. (北京师范大学化学学院 北京 100875)
  • 收稿日期:2007-08-18 修回日期:2007-11-07 出版日期:2008-03-14 发布日期:2008-03-14
  • 通讯作者: 丁万见

Theoretical Investigations on the Photolysis of Thiophene

ZHANG Wen-Yu, DING Wan-Jian*, LIU Ruo-Zhuang*   

  1. (College of Chemistry, Beijing Normal University, Beijing 100875)
  • Received:2007-08-18 Revised:2007-11-07 Online:2008-03-14 Published:2008-03-14
  • Contact: DING Wan-Jian

Density functional theory (B3LYP) along with 6-31G** and 6-31++G** basis sets was employed to investigate the photodissociation reactions of thiophene. According to the experiment results, five photolysis channels have been examined, including three closed-shell molecular channels yielding C4H4+S, C2H2+C2H2S, and CS+C3H4, and two radical channels yielding HCS+C3H3 and HS+C4H3. The most probable isomers of the product fragments were determined. It was found that the reaction yielding C4H4+S was the most energetically favorable in the triplet state and c-C4H4S→C2H2+C2H2S was preferential in the ground state. The calculation results show that C2H2+C2H2S, which were found to be the major products, were formed mainly in the ground state. By comparison of the computational results with the experimental findings, it can be concluded that the photodissociation mechanism of thiophene is dependent on the wave length.

Key words: thiophene, photodissociation, reaction mechanism, B3LYP