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Localized orbital corrections for density functional calculations on transition metal containing systems

机译：用于含过渡金属的系统的密度泛函计算的局部轨道校正

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摘要

We describe a method that improves density functional theory (DFT) calculations for transition metal containing systems via a set of empirical localized orbital corrections applied to the d-electron manifold of the metal (DBLOC). The method is an extension of the localized orbital approach that we have developed for first and second row atoms (DFT-LOC) which has demonstrated considerable success in correcting errors in gradient corrected and hybrid functionals. The most effective set of corrections are constructed using the B3LYP functional (B3LYP-DBLOC) but we have also investigated other functionals, which are similarly improved by the methodology. The method has initially been applied to benchmark data sets of octahedral complexes, which are used to calibrate the empirical correction parameters. For these data sets, mean unsigned errors of B3LYP-DBLOC are on the order of 1 kcal/mol for metal-ligand bond energies (as compared to 3.7 kcal/mol for uncorrected B3LYP), 2 kcal/mol for spin splittings (as compared to 10 kcal/mol for uncorrected B3LYP), and 0.12 eV for redox potentials (as compared to 0.40 eV for uncorrected B3LYP). The underlying rationale for the success of the LOCs, based on transferability of errors in DFT calculations for localized chemical groups across different molecules, is discussed, and the results for the various property calculations enumerated above are summarized. Applications to a number of complex systems, including titanium dioxide nanoparticles and several metalloenzymes, are presented, which demonstrate that the correction terms improve agreement with experiment in these systems. (C) 2017 Published by Elsevier B.V.
机译：我们描述了一种方法，该方法通过应用于金属的d电子流形（DBLOC）的一组经验性局部轨道校正来改善含过渡金属的系统的密度泛函理论（DFT）计算。该方法是我们针对第一行和第二行原子（DFT-LOC）开发的局部轨道方法的扩展，该方法已证明在校正梯度校正和混合函数的误差方面取得了巨大的成功。使用B3LYP功能（B3LYP-DBLOC）构建了最有效的校正集，但是我们还研究了其他功能，这些功能也被该方法进行了类似的改进。该方法最初已应用于八面体络合物的基准数据集，该数据集用于校准经验校正参数。对于这些数据集，金属配体键能的B3LYP-DBLOC平均无符号误差约为1 kcal / mol（相比之下，未经校正的B3LYP的平均无符号误差为3.7 kcal / mol），自旋分裂的平均无符号误差为2 kcal / mol（与对于未校正的B3LYP为10 kcal / mol）和对于氧化还原电势为0.12 eV（相比之下，未经校正的B3LYP为0.40 eV）。讨论了LOC成功的基本原理，该原理基于DFT计算中跨不同分子的局部化学基团中误差的可转移性，并总结了上面列举的各种性能计算的结果。介绍了在许多复杂系统中的应用，包括二氧化钛纳米颗粒和几种金属酶，这些证明了校正术语改善了与这些系统中实验的一致性。 （C）2017由Elsevier B.V.发布

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