Density Functional Method Studies of X H （X=C, N, O, Si, P, S） Bond Dissociation Energies

作     者：傅尧 董晓昱 王毅敏 刘磊 郭庆祥 

作者机构：DepartmentofChemistryUniversityofScienceandTechnologyofChinaHefeiAnhui230026 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：2005年第23卷第5期

页      面：474-482页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：the National Natural Science Foundation of China (. 20332020  20472079) 

主　　题：density functional theory bond dissociation energy basis set B3P86 method 

摘      要：The performances of the density functional theory (DFT) methods in calculating X  H bond dissociation energies (BDE, XC, N, O, Si, P, S) were evaluated. It was found that most DFT methods including B3LYP, B3PW91, G96LYP, PBE1PBE and BH&HLYP significantly underestimated the X  H BDE by as much as 13–24 kJ/mol. The underestimation is not due to the use of finite basis set, because the DFT methods still significantly underestimate the X  H BDE with the complete basis set. Therefore, these DFT methods can not be used to calculate the BDE directly. Nevertheless, the B3P86 method shows very small underestimation for the X  H BDE. Further analysis suggests that there be no advantage for using the restricted open‐shell DFT methods. The unrestricted DFT methods actually perform slightly better than the restricted open‐shell DFT methods in most cases. Finally, it was found that the underestimation by the DFT methods was largely systematic. The use of the calibrated UDFT/6‐311++G(d, p) method was recommended to calculate the X  H BDE.