Comment on “Anisotropic intermolecular interactions in van der Waals and hydrogen-bonded complexes: What can we get from density-functional calculations?” [J. Chem. Phys. 111, 7727 (1999)]
Comment on “Anisotropic intermolecular interactions in van der Waals and hydrogen-bonded complexes: What can we get from density-functional calculations?” [J. Chem. Phys. 111, 7727 (1999)]
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评论“范德华和氢键配合物中的各向异性分子间相互作用：我们可以从密度泛函计算中得到什么？”[J. Phys.
DOI：
10.1063/1.481955
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发表时间：
2000
影响因子：
4.4
通讯作者：
Tomasz A. Wesol owski
中科院分区：
文献类型：
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作者：
Tomasz A. Wesol owski
在这篇评论中，指出Milet等人[J.Chem.Phys.111，7727（1999）]所考虑的广义梯度近似（GGA）泛函共享显著违反Lieb-Oxford界限的相同交换部分（B88）。在弱重叠电子密度的情况下，违反该精确条件显示出导致交换能的显著误差[Wesol/owski等人，J. Phys. Chem. A 101，7818（1997）; Zhang等人，J. Chem.Phys.107，7921（1997）]。数值算例表明，这样的交换泛函，更好地满足Lieb-Oxford约束导致更好的相互作用能也由Milet等人研究的复合物。
In this comment, it is pointed out that the generalized gradient approximation (GGA) functionals considered by Milet et al. [ J. Chem. Phys. 111, 7727 (1999)] share the same exchange part (B88) which violates significantly the Lieb–Oxford bound. Violation of this exact condition was shown to result in significant errors of the exchange energy in the case of weakly overlapping electron densities [Wesol/owski et al., J. Phys. Chem. A 101, 7818 (1997); Zhang et al., J. Chem. Phys. 107, 7921 (1997)]. Numerical examples are given to illustrate that such exchange functionals which better satisfy the Lieb–Oxford bound lead to better interaction energies also for the complexes studied by Milet et al.