Acta Chimica Sinica ›› 2008, Vol. 66 ›› Issue (3): 362-370. Previous Articles     Next Articles

Original Articles

环境污染物中碳氯键离解能的理论研究

王华静,傅尧*,王晨,郭庆祥*   

  1. (中国科学技术大学化学系 合肥 230026)
  • 收稿日期:2007-05-25 修回日期:2007-07-05 出版日期:2008-02-14 发布日期:2008-02-14
  • 通讯作者: 傅尧

Theoretical Study of Homolytic C-Cl Bond Dissociation Enthalpies of Environmental Pollutants

WANG Hua-Jing ;FU Yao* ;WANG Chen; GUO Qing-Xiang*   

  1. (Department of Chemistry, University of Science and Technology of China, Hefei 230026)
  • Received:2007-05-25 Revised:2007-07-05 Online:2008-02-14 Published:2008-02-14
  • Contact: FU Yao

The bond dissociation enthalpies (BDEs) of the C-Cl bonds were calculated by using six density functional theory (DFT) methods (B3LYP, B3P86, MPW1K, TPSS1KCIS, X3LYP, BMK). The results were compared with the corresponding experimental values to examine the reliability of these methods. It was found that although some new methods developed in recent years were found to be superior to B3LYP method, they were not the best density functional methods for the calculation of the BDEs of C-Cl bonds. However the B3P86/6-311++G(2df, 2p) level of theory was found to be the most accurate, with an mean absolute deviation of 6 .58 kJ/mol for 17 C-Cl bonds. Finally, armed with the theoretical tool the C-Cl BDEs of some persistent environmental pollutants were calculated. The substituent effects were discussed.

Key words: homolytic bond dissociation enthalpies, biodegradation, chlorobenzene, chlorophenol