Heats of formation from DFT calculations: An examination of several parameterizations

被引：29

作者：

Guthrie, JP ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2001年 / 105卷 / 40期

关键词：

D O I：

10.1021/jp010355k

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

DFT calculations of the total energy of molecules (B3LYP/6-31G**//rhf/6-31G**) can be converted to enthalpies of formation by various new parametrization schemes. Three schemes follow the hierarchy proposed by Benson and Buss, of atom, bond, and group contributions. In addition, a modified atomic scheme was found to give better results than the atomic scheme with fewer parameters than the bond scheme. The lower level parametrizations could fit more compounds but had lower precision. To compare the schemes a standard set of 180 compounds was treated by all methods. The results are: Method, number of compounds, number of parameters, standard deviation (kcal/mol): Atom, full: 250, 18, 2.96; std: 180, 12, 2.64; Modified atom, full: 248, 23, 2.53, std: 180, 18, 1.97; Bond, full: 229, 40, 1.90; std: 180, 32, 1.72; Group, full: 183, 79, 1.39; std: 180, 79, 1.26.

引用

页码：9196 / 9202

页数：7

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