The accuracy of post-B3LYP functionals is analyzed using an open-shell database of Cu(II) dinuclear complexes with well-defined experimental values of the magnetic coupling constants. This database provides a sound open-shell training set to be used to improve the fitting schemes in defining new functionals or when reparametrizing the existing ones. For a large set of representative hybrid exchange-correlation functionals, it is shown that the overall description of moderate-to-strong antiferromagnetic interactions is significantly more accurate than the description of ferromagnetic or weakly antiferromagnetic interactions. In the case of global hybrids, the most reliable ones have 25–40% Fock exchange with SOGGA and PBE0 being the most reliable and M06 the exception. For range-corrected hybrids, the long-range corrected CAM-B3LYP and ωB97XD provide acceptable results, and M11 is comparable but more erratic. It is concluded that the reliability of the calculated values is system- and range-dependent, and this fact introduces a serious warning on the blind use of a single functional to predict magnetic coupling constants. Hence, to extract acceptable magnetostructural correlations, a “standardization” of the method to be used is advised to choose the optimal functional.

中文翻译：

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B3LYP后功能不能改善Cu（II）双核络合物中磁耦合的描述。

使用具有明确定义的磁耦合常数实验值的Cu（II）双核配合物的开放式数据库，分析了B3LYP后功能的准确性。该数据库提供了一个完善的开放式培训集，可用于改进在定义新功能时或在重新设置现有功能时的拟合方案。对于大量代表性的混合交换相关函数，表明中到强反铁磁相互作用的总体描述比铁磁或弱反铁磁相互作用的描述更为准确。对于全球混合动力车，最可靠的混合动力车有25-40％的Fock交换，其中SOGGA和PBE0最可靠，而M06除外。对于范围校正的混合动力车，远程校正的CAM-B3LYP和ωB97XD提供了可接受的结果，M11具有可比性，但更不稳定。结论是，计算值的可靠性与系统和范围有关，并且这一事实对盲目使用单个函数预测磁耦合常数提出了严重警告。因此，为了提取可接受的磁结构相关性，建议对要使用的方法进行“标准化”以选择最佳功能。