Zhao Chaoyue, Wu Rongkai, Zhang Shuoqing, Hong Xin
Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, P. R. China.
Beijing National Laboratory for Molecular Sciences, No. 2, Zhongguancun North First Street, Beijing 100190, P. R. China.
J Phys Chem A. 2023 Aug 17;127(32):6791-6803. doi: 10.1021/acs.jpca.3c04215. Epub 2023 Aug 2.
The current benchmark study is focused on determining the most precise theoretical method for optimizing the geometry of transition metal-dinitrogen complexes. To accomplish this goal, seven density functional (DF) methods from five distinct classes of density functional theory (DFT) have been selected, including B3LYP-D3(BJ), BP86-D3(BJ), PBE0-D3(BJ), ωB97X-D, M06, M06-L, and TPSSh-D3(BJ). These DFs will be utilized with the Karlsruhe basis set (def2-SVP). To carry out this benchmark study, a total of forty-two structurally diverse transition metal-dinitrogen compounds with experimentally known X-ray data have been selected from the Cambridge Crystallographic Data Centre (CCDC). Based on a comparison of the theoretical data with experimental values (X-ray) of the selected transition metal-dinitrogen compounds, statistical parameters such as root-mean-square deviation (RMSD) and N-N and M-N bond lengths are obtained to evaluate the performance of the seven chosen DFs. According to the obtained results, among all DFT methods used in the study, Minnesota functionals (M06 and M06-L) and TPSSh-D3(BJ) show good performance, with lower RMSD values. This suggests that these three methods are the most reliable for optimizing the geometry of transition metal-dinitrogen complexes. Based on the absolute errors of the N-N and M-N bond lengths relative to the X-ray data, further analysis is conducted, and it is determined that M06-L is the best functional for optimizing the geometry of transition metal-dinitrogen compounds. Additionally, the influence of using a high-level basis set (def2-TZVP) compared to def2-SVP on the calculated RMSD among the seven chosen methods is found to be negligible.
当前的基准研究聚焦于确定优化过渡金属 - 二氮配合物几何结构的最精确理论方法。为实现这一目标，从密度泛函理论（DFT）的五个不同类别中选取了七种密度泛函（DF）方法，包括B3LYP - D3(BJ)、BP86 - D3(BJ)、PBE0 - D3(BJ)、ωB97X - D、M06、M06 - L和TPSSh - D3(BJ)。这些密度泛函将与卡尔斯鲁厄基组（def2 - SVP）一起使用。为开展此基准研究，已从剑桥晶体学数据中心（CCDC）选取了总共42种结构多样且具有实验已知X射线数据的过渡金属 - 二氮化合物。基于所选过渡金属 - 二氮化合物的理论数据与实验值（X射线）的比较，获得诸如均方根偏差（RMSD）以及N - N和M - N键长等统计参数，以评估所选择的七种密度泛函的性能。根据所得结果，在该研究中使用的所有DFT方法中，明尼苏达泛函（M06和M06 - L）以及TPSSh - D3(BJ)表现良好，具有较低的RMSD值。这表明这三种方法在优化过渡金属 - 二氮配合物的几何结构方面最为可靠。基于N - N和M - N键长相对于X射线数据的绝对误差进行了进一步分析，确定M06 - L是优化过渡金属 - 二氮化合物几何结构的最佳泛函。此外，发现与def2 - SVP相比，使用高级基组（def2 - TZVP）对所选七种方法计算的RMSD的影响可忽略不计。
