Universal Correction of Density Functional Theory to Include London Dispersion (up to Lr, Element 103)
Universal Correction of Density Functional Theory to Include London Dispersion (up to Lr, Element 103)
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DOI：
10.1021/jz2016395
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发表时间：
2012-02-02
影响因子：
5.7
通讯作者：
Goddard, William A., III
中科院分区：
文献类型：
--
作者：
Kim, Hyungjun;Choi, Jeong-Mo;Goddard, William A., III
传统的密度泛函理论 (DFT) 无法准确描述伦敦色散，而伦敦色散对于描述软物质（生物系统、聚合物、核酸）和分子晶体中的分子相互作用至关重要。这导致了几种将原子相关势添加到 Kohn-Sham DFT 能量中的方法。其中一些修正适合准确的量子力学结果，但确定描述周期表中所有原子的适当参数将是乏味的。我们提出了一种替代方法，其中低梯度（lg）函数形式的单个参数与为整个周期表（直到 Lr，Z = 103）开发的基于规则的 UFF（通用力场）非键参数相结合，称为 DFT-ulg 方法。我们表明，DFT-ulg 方法可以非常准确地描述分子配合物和分子晶体的性质，为更准确地预测整个元素周期表中的弱相互作用提供了方法。
Conventional density functional theory (DFT) fails to describe accurately the London dispersion essential for describing molecular interactions in soft matter (biological systems, polymers, nucleic acids) and molecular crystals. This has led to several methods in which atom-dependent potentials are added into the Kohn-Sham DFT energy. Some of these corrections were fitted to accurate quantum mechanical results, but it will be tedious to determine the appropriate parameters to describe all of the atoms of the periodic table. We propose an alternative approach in which a single parameter in the low-gradient (lg) functional form is combined with the rule-based UFF (universal force-field) nonbond parameters developed for the entire periodic table (up to Lr, Z = 103), named as a DFT-ulg method. We show that DFT-ulg method leads to a very accurate description of the properties for molecular complexes and molecular crystals, providing the means for predicting more accurate weak interactions across the periodic table.