Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory
Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory
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DOI：
10.1002/cphc.201701334
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发表时间：
2018-04-17
期刊：
影响因子：
2.9
通讯作者：
Cramer, Christopher J.
中科院分区：
文献类型：
--
作者：
Dereli, Busra;Ortuno, Manuel A.;Cramer, Christopher J.
铜无处不在，其单电子氧化还原化学是许多催化过程的核心。对此类化学进行建模需要电子结构方法能够准确预测化合物的电离能 (IE)，其中包括处于不同氧化态并由各种配体支持的铜的化合物。在此，我们利用 21 个现代密度泛函和 DLPNO-CCSD(T) 波函数理论模型估计了文献中先前报道的 12 个单核 Cu 物种的 IE；我们考虑后者的外推值以提供可接受精度的参考值。我们的结果揭示了功能表现的相当大的多样性。尽管几乎总是有至少一个函数对于任何给定物种表现良好，但没有一个函数对于测试集的每个成员都表现良好，并且某些情况特别病态。在整个测试集上，SOGGA11-X 函数表现最佳，平均无符号误差 (MUE) 为 0.22eV。 PBE0、B97X-D、CAM-B3LYP、M11-L、B3LYP 和 M11 的 MUE 范围在 0.23 至 0.34eV 之间。当将相对论效应纳入零阶正则近似时，B97X-D、CAM-B3LYP 和 PBE0 被发现可提供最佳精度。
Copper is ubiquitous and its one-electron redox chemistry is central to many catalytic processes. Modeling such chemistry requires electronic structure methods capable of the accurate prediction of ionization energies (IEs) for compounds including copper in different oxidation states and supported by various ligands. Herein, we estimate IEs for 12 mononuclear Cu species previously reported in the literature by using 21 modern density functionals and the DLPNO-CCSD(T) wave function theory model; we consider extrapolated values of the latter to provide reference values of acceptable accuracy. Our results reveal a considerable diversity in functional performance. Although there is nearly always at least one functional that performs well for any given species, there are none that do so for every member of the test set, and certain cases are particularly pathological. Over the entire test set, the SOGGA11-X functional performs best with a mean unsigned error (MUE) of 0.22eV. PBE0, B97X-D, CAM-B3LYP, M11-L, B3LYP, and M11 exhibit MUEs ranging between 0.23 and 0.34eV. When including relativistic effects with the zero-order regular approximation, B97X-D, CAM-B3LYP, and PBE0 are found to provide the best accuracy.