Local hybrid functionals containing strong-correlation factors (scLHs) and range-separated local hybrids (RSLHs) have been integrated into an efficient coupled-perturbed Kohn–Sham implementation for the calculation of nuclear shielding constants. Several scLHs and the ωLH22t RSLH have then been evaluated for the first time for the extended NS372 benchmark set of main-group shieldings and shifts and the TM70 benchmark of 3d transition-metal shifts. The effects of the strong-correlation corrections have been analyzed with respect to the spatial distribution of the sc-factors, which locally diminish exact-exchange admixture at certain regions in a molecule. The scLH22t, scLH23t-mBR, and scLH23t-mBR-P functionals, which contain a “damped” strong-correlation factor to retain the excellent performance of the underlying LH20t functional for weakly correlated situations, tend to make smaller corrections to shieldings and shifts than the “undamped” scLH22ta functional. While the latter functional can also deteriorate agreement with the reference data in certain weakly correlated cases, it provides overall better performance, in particular for systems where static correlation is appreciable. This pertains only to a minority of systems in the NS372 main-group test set but to many more systems in the TM70 transition-metal test set, in particular for high-oxidation-state complexes, e.g., Cr(+VI) complexes and other systems with stretched bonds. Another undamped scLH, the simpler LDA-based scLH21ct-SVWN-m, also tends to provide significant improvements in many cases. The differences between the functionals and species can be rationalized on the basis of one-dimensional plots of the strong-correlation factors, augmented by isosurface plots of the fractional orbital density (FOD). Position-dependent exact-exchange admixture is thus shown to provide substantial flexibility in treating response properties like NMR shifts for both weakly and strongly correlated systems.

中文翻译：

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用于计算 NMR 屏蔽和位移的强相关校正局部混合泛函的实现和首次评估

包含强相关因子 (scLH) 和范围分离局部混合 (RSLH) 的局部混合泛函已集成到高效的耦合扰动 Kohn-Sham 实现中，用于计算核屏蔽常数。然后，首次针对主族屏蔽和位移的扩展 NS372 基准集以及 3d 过渡金属位移的 TM70 基准对几个 scLH 和 ωLH22t RSLH 进行了评估。强相关校正的影响已针对 sc 因子的空间分布进行了分析，该因子局部减少了分子中某些区域的精确交换混合物。 scLH22t、scLH23t-mBR 和 scLH23t-mBR-P 泛函包含“阻尼”强相关因子，以在弱相关情况下保留基础 LH20t 泛函的优异性能，与屏蔽和偏移相比，它往往对屏蔽和偏移进行较小的修正“无阻尼”scLH22ta 泛函。虽然后一个函数在某些弱相关情况下也会降低与参考数据的一致性，但它提供了总体更好的性能，特别是对于静态相关性明显的系统。这仅适用于 NS372 主组测试集中的少数系统，但适用于 TM70 过渡金属测试集中的更多系统，特别是高氧化态配合物，例如 Cr(+VI) 配合物和其他具有拉伸键的系统。另一种无阻尼 scLH，即更简单的基于 LDA 的 scLH21ct-SVWN-m，在许多情况下也往往会提供显着的改进。泛函和物种之间的差异可以在强相关因子的一维图的基础上合理化，并通过分数轨道密度（FOD）的等值面图进行增强。因此，位置依赖的精确交换混合物在处理弱相关系统和强相关系统的 NMR 位移等响应特性方面提供了很大的灵活性。