Assessment of Newest Meta-GGA Hybrids for Late Transition Metal Reactivity: Fractional Charge and Fractional Spin Perspective

Abstract

In recent years there has been a significant interest of DFT community in the development of new (hybrid) meta-generalized gradient approximations (meta-GGAs), including range-separated hybrids. The new DFT methods, e.g., SCAN, SCAN0, ωB97M-V, and our own LC-PBETPSS-D3 promise an improvement over well-established models, such as, PBE, PBE0, ωB97X-D, and the M06-type functionals. However, the tests published to date cover only main-group chemistry. This work fills this gap by examining reactivity of model systems, such as gold-ligand complexes, Pd and Ni insertion reactions into covalent bonds, and the pathway for olefin metathesis by a model Grubbs system, all of which include late transition metals. In the attempt to rationalize the performance of functionals, we study the fractional charge and fractional spin errors of the Au atom and the Au7 cluster. While we find the main qualitative issues of DFT are not yet solved, the introduction of meta-GGA ingredients yields a notable improvement makeing the new meta-GGAs the preferred choice for transition-metal chemistry.

First-Principles Calculation of Transition Metal Hyperfine Coupling Constants with the Strongly Constrained and Appropriately Normed (SCAN) Density Functional and its Hybrid Variants

“…The SCAN functional has inspired a series of recent studies that investigated the definition of simple hybrid as well as double-hybrid functionals using SCAN as the basic mGGA component [28,29,31]. As an example, SCAN0 [29], a hybrid with 25% exact exchange, has been reported to offer improved performance for a variety of properties, including reaction energetics of late transition metal systems [31]. In this vein, we additionally studied for the spectroscopic property of interest the performance of the already described SCAN0 functional, and of the SCANh functional defined in the present study, a hybrid with 10% exact exchange.…”

“…Studies that examined the performance of SCAN and certain derivative functionals have already indicated that it performs well for a variety of energy-related properties, usually surpassing previous GGA and mGGA approaches [22][23][24][25][26][27][28][29][30][31]. However, it is unclear whether these advances also translate into improved description of the physical mechanisms that give rise to the distinct contributions to hyperfine coupling.…”

Reactivity of arsenoplatin complex versus water and thiocyanate: a DFT benchmark study

“…It is nowadays commonly accepted that evaluation of the performance of density functionals through assessment on different realistic chemical models is a crucial step prior to the investigation of new systems. Though there is a plethora of studies on the performance of DFT functionals [33][34][35] on main group elements, only more recently density functionals have been benchmarked in many studies involving big datasets to assess their predictive capability in describing the most common transition metal reactions [36][37][38]. However, the accuracy of the wide range of newly developed density functionals has been found to depend both on the kind of considered transition metals (early, late, first or second and third row, etc.)…”

Multiwavelets Applied to Metal-Ligand Interactions: Energies Free from Basis Set Errors

“…3,4,5,6,7,8,9,10 The difficulty of contemporary DFT functionals to accurately compute metal-ligand interactions has been highlighted in the literature. 11,12,13,14,15,16,17,18,19,20,21,22 Many of the reported studies focus on the performance of different DFT functionals and the importance of including dispersion corrections in the computed energies. 11,15 There is less focus on the importance of choosing an adequate basis set.…”