Assessment of Contemporary Theoretical Methods for Bond Dissociation Enthalpies  

键解离焓的理论方法研究

作　　者：李璐[1,2] 樊红军[2] 胡浩权[1] 李璐;樊红军;胡浩权(大连理工大学化工学院,煤化工研究设计所,精细化工国家重点实验室,大连116024;中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连116023)

机构地区：[1]大连理工大学化工学院,煤化工研究设计所,精细化工国家重点实验室,大连116024 [2]中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连116023

出　　处：《Chinese Journal of Chemical Physics》2016年第4期453-461,I0001,I0002,共11页化学物理学报（英文）

摘　　要：The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.

关 键 词：Bond dissociation enthalpies Density functional theory Double-hybrid density functional theory High-level composite methods 

分 类 号：O4[理学—物理]