Density functional theory including dispersion corrections for intermolecular interactions in a large benchmark set of biologically relevant molecules
Density functional theory including dispersion corrections for intermolecular interactions in a large benchmark set of biologically relevant molecules
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DOI：
10.1039/b612585a
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发表时间：
2006-01-01
影响因子：
3.3
通讯作者：
Grimme, Stefan
中科院分区：
文献类型：
--
作者：
Antony, Jens;Grimme, Stefan
采用包含色散修正的密度泛函理论（DFT-D）计算了主要由DNA碱基对和氨基酸对组成的广泛基准组中的分子间相互作用能，CCSD（T）完全基组极限估计可用于该基准组（JSCH-2005数据库）。对三种广义梯度近似（GGA）密度泛函B-LYP、PBE和新的B 97-D以及流行的混合泛函B3-LYP进行了测试。DFT-D相互作用能平均偏离参考值小于1 kcal mol（-1）或10%。在161例中，只有6例的偏差超过2 kcal mol（-1）。除了一个例外，少数较大的偏差发生在从实验几何形状中提取的非平衡结构。最大的绝对偏差被观察到的对相反电荷的氨基酸，然而，不显着的相对基础上，由于巨大的相互作用能> 100 kcal mol（-1）的参与。使用三重zeta AO基组对基组叠加误差的平衡（CP）校正在0和-1 kcal mol（-1）之间变化（在大多数情况下<相互作用能的5%），但四种复合物除外，其高达-1.4 kcal mol（-1）。因此，建议在具有合理基组的DFT-D处理中跳过CP校正的费力计算。所考虑的三种色散校正的GGA的不同之处主要在于氢键DNA碱基对的相互作用，在B 97-D的情况下，它们系统地太小了0.6 kcal mol（-1），而对于PBE-D，它们太高了1.5 kcal mol（-1），对于B-LYP-D，它们太高了0.5 kcal mol（-1）。所有在所有优秀的结果，已经获得了负担得起的计算成本表明DFT-D方法是一个常规的工具，在有机化学或生物化学的许多应用。
Density functional theory including dispersion corrections (DFT-D) is applied to calculate intermolecular interaction energies in an extensive benchmark set consisting mainly of DNA base pairs and amino acid pairs, for which CCSD(T) complete basis set limit estimates are available (JSCH-2005 database). The three generalized gradient approximation (GGA) density functionals B-LYP, PBE and the new B97-D are tested together with the popular hybrid functional B3-LYP. The DFT-D interaction energies deviate on average by less than 1 kcal mol(-1) or 10% from the reference values. In only six out of 161 cases, the deviation exceeds 2 kcal mol(-1). With one exception, the few larger deviations occur for non-equilibrium structures extracted from experimental geometries. The largest absolute deviations are observed for pairs of oppositely charged amino acids which are, however, not significant on a relative basis due to the huge interaction energies > 100 kcal mol(-1) involved. The counterpoise (CP) correction for the basis set superposition error with the applied triple-zeta AO basis sets varies between 0 and -1 kcal mol(-1) (< 5% of the interaction energy in most cases) except for four complexes, where it is up to -1.4 kcal mol(-1). It is thus suggested to skip the laborious calculation of the CP correction in DFT-D treatments with reasonable basis sets. The three dispersion corrected GGAs considered differ mainly for the interactions of the hydrogen-bonded DNA base pairs, which are systematically too small by 0.6 kcal mol(-1) in case of B97-D, while for PBE-D they are too high by 1.5 kcal mol(-1), and for B-LYP-D by 0.5 kcal mol(-1). The all in all excellent results that have been obtained at affordable computational costs suggest the DFT-D method to be a routine tool for many applications in organic chemistry or biochemistry.