Interaction energies of van der Waals and hydrogen bonded systems calculated using density functional theory: Assessing the PW91 model
Interaction energies of van der Waals and hydrogen bonded systems calculated using density functional theory: Assessing the PW91 model
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DOI：
10.1063/1.1344891
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发表时间：
2001-02
影响因子：
4.4
通讯作者：
S. Tsuzuki;H. Lüthi
中科院分区：
文献类型：
--
作者：
S. Tsuzuki;H. Lüthi
基于对氖气、氩气、甲烷、乙烯和苯二聚体以及 12 种氢键配合物（水、甲醇、甲酸、氟化氢、氨、甲酰胺二聚体和 水-甲醇、水-二甲醚、水-甲醛、氰化氢-氟化氢、水-氨、水-甲酰胺络合物）。将结果与 Becke 交换和 Lee、Yang 和 Parr 相关泛函 (BLYP)、Becke 3 参数泛函与 Lee、Yang 和 Parr 相关泛函 (B3LYP)、二阶 Mo/ller-Plesset 摄动 (MP2) 以及使用单次和双次替换以及非迭代三重校正的耦合簇计算获得的结果进行了比较 [CCSD(T)] 计算。计算的相互作用能表明，PW91 泛函的性能比 BLYP 或 B3LYP 泛函好得多。在最坏的情况下，计算出的氢键配合物的结合能误差为 20%。最苛刻的情况是对结合能具有较大色散贡献的系统，例如苯二聚体。与无法解释色散的 BLYP 和 B3LYP 泛函相反，PW91 泛函至少部分恢复了吸引力。与 MP2 和 CCSD(T) 方法相比，PW91 泛函的基组依赖性相对较小。尽管在色散相互作用方面偶尔会遇到困难，但 PW91 泛函可能是从头计算方法的可行替代方法，尤其是在研究大型配合物的情况下。
The performance of density functional theory using the Perdew and Wang’s exchange and correlation functionals (PW91) functional for the prediction of intermolecular interactionenergies is evaluated based on calculations on the neon, argon, methane, ethylene, and benzene dimers, as well as on 12 hydrogen bonded complexes (water, methanol, formic acid, hydrogen fluoride, ammonia, formamide dimers and water–methanol, water–dimethyl ether, water–formaldehyde, hydrogen cyanide–hydrogen fluoride, water–ammonia, water–formamide complexes). The results were compared with those obtained from Becke’s exchange and Lee, Yang, and Parr’s correlation functionals (BLYP), Becke’s 3 parameter functional combined with Lee, Yang, and Parr’s correlation functional (B3LYP), second order Mo/ller–Plesset perturbation (MP2), and coupled cluster calculations with single and double substitutions and with non-iterative triple corrections [CCSD(T)] calculations. The calculated interactionenergies show that the PW91 functional performs much better than the BLYP or B3LYP functionals. The error in the computed binding energies of the hydrogen bonded complexes is 20% in the worst case. The most demanding cases are the systems with large dispersion contributions to the binding energy, such as the benzene dimer. In contrast to the BLYP and B3LYP functionals which fail to account for dispersion, the PW91 functional at least partly recovers the attraction. The basis set dependence of the PW91 functionals is relatively small in contrast to the MP2 and CCSD(T) methods. Despite its occasional difficulties with dispersion interaction, the PW91 functional may be a viable alternative to the ab initio methods, certainly in situations where large complexes are being studied.