Winget Paul, Clark Timothy
Computer-Chemie-Centrum, Universität Erlangen-Nürnberg, Nägelsbachstrasse 25, 91052 Erlangen, Germany.
J Comput Chem. 2004 Apr 15;25(5):725-33. doi: 10.1002/jcc.10398.
We have calculated the geometries, energies, and normal vibrations of 845 compounds containing the elements H, C, N, O, F, Al, Si, P, S, and Cl using hybrid density functional theory in order to investigate the accuracy of atom-additive schemes for predicting enthalpies of formation at 298 K. The results give a more realistic estimate of the accuracy of density functional calculations than some overoptimistic earlier correlations. We have also calculated atom-additive schemes for the zero-point energies and enthalpic corrections to the energies. Remarkably, it is not important to include the vibrational or rotational contributions, which can be estimated well within a purely Born-Oppenheimer regression model.
我们使用杂化密度泛函理论计算了845种含有氢、碳、氮、氧、氟、铝、硅、磷、硫和氯元素的化合物的几何结构、能量和正常振动，以研究原子加和方案预测298K时生成焓的准确性。与一些过于乐观的早期关联相比，结果对密度泛函计算的准确性给出了更现实的估计。我们还计算了零点能量和能量的焓校正的原子加和方案。值得注意的是，包含振动或转动贡献并不重要，这些贡献可以在纯玻恩-奥本海默回归模型中得到很好的估计。
