论文标题
在两种类型的离域化误差中,配体添加性和发散趋势来自近似密度功能理论
Ligand Additivity and Divergent Trends in Two Types of Delocalization Errors from Approximate Density Functional Theory
论文作者
论文摘要
尽管使用了广泛使用,但密度功能理论(DFT)的预测准确性受到离域误差的阻碍,尤其是对于过渡金属复合物等相关系统。已经开发了两种互补的调整策略来减少定位误差:消除对电荷添加或去除的全局曲率,并计算线性响应Hubbard U作为固定电荷的金属中心处局部曲率的量度,并将其应用于ADFT+U框架中的过渡金属复合物。当我们通过改变一系列杂型复合物中的强场配体的数量或通过几何限制同性恋八人体内复合物中的金属 - 配体键长,我们研究了两种定位误差测量误差的关系之间的关系。我们表明,在这些具有不同配体磁场的复合物中,全球和局部曲率之间通常存在逆关系。我们发现配体取代对两种定位量度的影响通常是加性的,但是两量很少重合。配体添加性的观察表明,有机会评估均质复合物上的误差以推断低对称复合物的校正。
Despite its widespread use, the predictive accuracy of density functional theory (DFT) is hampered by delocalization errors, especially for correlated systems such as transition-metal complexes. Two complementary tuning strategies have been developed to reduce delocalization error: eliminating the global curvature with respect to charge addition or removal, and computing a linear response Hubbard U as a measure of local curvature at the metal center at fixed charge and applying it to the transition-metal complex in a DFT+U framework. We investigate the relationship between the two measures of delocalization error as we manipulate the ligand field strength by varying the number of strong-field ligands in a series of heteroleptic complexes or by geometrically constraining the metal-ligand bond length in homoleptic octahedral complexes. We show that across these sets of complexes with varying ligand fields, an inverse relationship generally exists between global and local curvatures. We find that effects of ligand substitution on both measures of delocalization are typically additive, but the two quantities seldom coincide. The observation of ligand additivity suggests opportunities for evaluating errors on homoleptic complexes to infer corrections for lower-symmetry complexes.