We have assessed the accuracy for magnetic properties of a set of 51 density functional approximations, including both recently published as well as already established functionals. The accuracy assessment considers a series of 27 small molecules and is based on comparing the predicted magnetizabilities to literature reference values calculated using coupled cluster theory with full singles and doubles and perturbative triples [CCSD(T)] employing large basis sets. The most accurate magnetizabilities, defined as the smallest mean absolute error, were obtained with the BHandHLYP functional. Three of the six studied Berkeley functionals and the three range-separated Florida functionals also yield accurate magnetizabilities. Also some older functionals like CAM-B3LYP, KT1, BHLYP (BHandH), B3LYP and PBE0 perform rather well. In contrast, unsatisfactory performance was generally obtained with Minnesota functionals, which are therefore not recommended for calculations of magnetically induced current density susceptibilities, and related magnetic properties such as magnetizabilities and nuclear magnetic shieldings.
We also demonstrate that magnetizabilities can be calculated by numerical integration of the magnetizability density; we have implemented this approach as a new feature in the gauge-including magnetically induced current method (GIMIC). Magnetizabilities can be calculated from magnetically induced current density susceptibilities within this approach even when analytical approaches for magnetizabilities as the second derivative of the energy have not been implemented. The magnetizability density can also be visualized, providing additional information that is not otherwise easily accessible on the spatial origin of the magnetizabilities.
Critical Benchmarking of the G4(MP2) Model, the Correlation Consistent Composite Approach and Popular Density Functional Approximations on a Probabilistically Pruned Benchmark Dataset of Formation Enthalpies
Benchmarking Basis Sets for Density Functional Theory Thermochemistry Calculations: Why unpolarised basis sets and the polarised 6-311G family should be avoided
Benchmarking and contrasting exchange-correlation functional differences in response to static correlation in unrestricted Kohn-Sham and a hybrid 1-electron reduced density matrix functional theory
Benchmarking of Oxygen Adsorption using TPD Spectroscopy for Accurate DFT Prediction of ORR on Anatase Titanium Dioxide (101)
The Institute for Solid State Physics, The University of Tokyo（东京大学固体离子体研究所）；Academic Assembly (Faculty of Science), Yamagata University（山形大学理学部）；RIKEN（理化学研究所）
Benchmarking theoretical electronic structure methods with photoemission orbital tomography
在过去的十年中，光电子发射轨道层析成像（POT）已经发展成为一个强大的工具，研究吸附在（金属）表面的有机分子的电子结构。通过测量光电子的角分布作为结合能的函数，并利用分子轨道的动量空间特征，POT导致在有机/金属界面的电子态密度的轨道分辨图像。在这一结合实验和理论的工作中，我们应用POT的原型有机$π$共轭分子双蒽（C $_{28}$ H $_{14}$），形成一个高度取向的单层铜（110）表面。在实验上，我们确定了前所未有的13个$π$和12个$σ$轨道的双蒽，并测量了它们各自的结合能和光谱线型在双蒽/Cu（110）界面。从理论上讲，我们执行密度泛函计算这个接口采用四个广泛使用的交换相关泛函的广义梯度近似的家庭，以及全球和范围分离的混合泛函。通过分析轨道投影态密度的电子结构，我们得到了详细的理论与实验的轨道评估。这使我们能够基准性能的调查功能方面的能力占轨道能量排列在有机/金属界面。
