Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
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DOI：
10.1021/ct200866d
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发表时间：
2012-02-01
影响因子：
5.5
通讯作者：
Truhlar, Donald G.
中科院分区：
文献类型：
--
作者：
Marenich, Aleksandr V.;Jerome, Steven V.;Truhlar, Donald G.
我们提出了一种新的方法来推导部分原子电荷的人口分析。新的模型，称为电荷模型5（CM 5），产生IV类部分原子电荷的映射从赫什菲尔德人口密度泛函电子电荷分布分析。CM 5模型利用了一组参数，这些参数是通过拟合614种分子结构的气相偶极矩的参考值而得到的。一个额外的测试集（不包括在CM 5参数化）包含107个单电荷离子与非零偶极矩，计算从准确的电子电荷密度，相对于核电荷的中心。CM 5模型适用于由气相或溶液中的周期表中的任何元素组成的任何带电或不带电分子。CM 5模型预测的被测分子的偶极矩平均比原始Hirshfeld方法或许多其他流行的方案（包括原子极性张量和Lowdin，Mulliken和自然人口分析）更准确。此外，CM 5电荷模型基本上独立于基组。它可以与更大的基组一起使用，因此该模型显着改进了我们以前的电荷模型CMx（x = 1-4或4 M）和其他易于基组敏感性的方法。CM 5部分原子电荷的构象依赖性比那些来自静电势。CM 5模型不会像静电拟合方案那样，对较大分子中的掩埋原子产生病态。CM 5模型可以与任何水平的电子结构理论（Hartree-Fock，post-Hartree-Fock和其他波函数相关方法或密度泛函理论）一起使用，只要可以为该理论水平计算精确的电子电荷分布和Hirshfeld分析。
We propose a novel approach to deriving partial atomic charges from population analysis. The new model, called Charge Model 5 (CM5), yields class IV partial atomic charges by mapping from those obtained by Hirshfeld population analysis of density functional electronic charge distributions. The CM5 model utilizes a single set of parameters derived by fitting to reference values of the gas-phase dipole moments of 614 molecular structures. An additional test set (not included in the CM5 parametrization) contained 107 singly charged ions with nonzero dipole moments, calculated from the accurate electronic charge density, with respect to the center of nuclear charges. The CM5 model is applicable to any charged or uncharged molecule composed of any element of the periodic table in the gas phase or in solution. The CM5 model predicts dipole moments for the tested molecules that are more accurate on average than those from the original Hirshfeld method or from many other popular schemes including atomic polar tensor and Lowdin, Mulliken, and natural population analyses. In addition, the CM5 charge model is essentially independent of a basis set. It can be used with larger basis sets, and thereby this model significantly improves on our previous charge models CMx (x = 1-4 or 4M) and other methods that are prone to basis set sensitivity. CM5 partial atomic charges are less conformationally dependent than those derived from electrostatic potentials. The CM5 model does not suffer from ill conditioning for buried atoms in larger molecules, as electrostatic fitting schemes sometimes do. The CM5 model can be used with any level of electronic structure theory (Hartree-Fock, post-Hartree-Fock, and other wave function correlated methods or density functional theory) as long as an accurate electronic charge distribution and a Hirshfeld analysis can be computed for that level of theory.