环境污染物中碳氯键离解能的理论研究TheoreticalStudyofHomolytic.PDF

2008 66 Vol. 66, 2008 年第 卷 化 学 学 报 3 , 362 370 ACTA CHIMICA SINICA No. 3, 362 370 第 期 ～ ～ ·研究论文· 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* ( 中国科学技术大学化学系 合肥 230026) 摘要 利用6 种密度泛函理论方法(B3LYP, B3P86, MPW1K, TPSS1KCIS, X3LYP, BMK)对碳氯键离解能进行理论计 算. 结果发现几种新发展的密度泛函(DFT)方法用于碳氯键离解能的计算比传统的 B3LYP 有较大的改善, 其中对能量 估算相对准确的B3P86 方法对碳氯键离解能的计算精度最高, 对17个分子中碳氯键离解能计算的平均绝对偏差为6.58 最后运用 方法对一系列环境危害较大 但可通过光化学降解和生物降解的氯代有机物的碳氯键离解能 kJ/mol. B3P86 , 值进行预测, 并讨论了影响碳氯键离解能的结构性质关系. 关键词 键离解能; 生物降解; 氯苯; 氯苯酚 Theoretical Study of Homolytic C—Cl Bond Dissociation Enthalpies of Environmental Pollutants WANG, Hua-Jing FU, Yao* WANG, Chen GUO, Qing-Xiang* (Department of Chemistry, University of Science and Technology of China, Hefei 230026) Abstract The bond dissociation enthalpies (BDEs) of the C—Cl bonds were calculated by using six den- sity 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 mo