Benchmark Study of Density Functional Theory Methods in Geometry Optimization of Transition Metal–Dinitrogen Complexes

Abstract

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-meansquare 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.

Triphasic circularly polarized luminescence switch quantum simulation of a topologically chiral catenane

“…From a computational point of view, taking note of this precise dynamism between the three co-conformations, it intuitively emerges that the chiroptical properties are greatly dependent on the location of the molecular system within the hypersurface of potential energy. 32,33 In density functional theory, the quality of the energy-optimized conformations is significantly affected by the choice of the exchange–correlation functionals, 34,35 whose performances are generally ranked by virtue of benchmarks targeting the accurate prediction of X-ray preferential conformations. 36–38 As a consequence of the lack of the single crystal X-ray data for the catenane depicted in Fig.…”

DFT Struggles to Predict the Energy Landscape for Iron Pyridine Diimine-Catalyzed [2 + 2] Cycloaddition of Alkenes: Insights into the Problem and Alternative Solutions

“…All computational calculations were executed utilizing the ORCA quantum chemical software package, version 5.0.3. , The geometries of all minima and transition states were fully optimized in the gas phase, using the TPSSh , density functional in conjunction with the def2-SVP basis set. The selection of this particular functional was driven by its superior performance in comparison to other functionals in delivering accurate geometries and energetics for first-row transition metal complexes. − All Density functional theory (DFT) calculations utilized the unrestricted Kohn–Sham (UKS) formalism and total charge = 0 . RIJCOSX approximation was employed to expedite the calculations.…”

MolBar: A Molecular Identifier for Inorganic and Organic Molecules with Full Support of Stereoisomerism

“…However, structural differences between identical fragments of the same molecule may remain due to variations attributable to different sources of the coordinates provided. For example, the application of different DFT functionals in a geometry optimization may result in different bond lengths, angles, and dihedral angles for the same molecule [37][38][39].…”