DFT-D4counterparts of leadingmeta-generalized-gradient approximation and hybrid density functionals for energetics and geometries

Abstract

Previously, we introduced DFT-D3(BJ)ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Goerigk, J Chem. Theory Comput. 2018, 14, 5725]. In this study, we present DFT-D4 damping parameters to build the DFT-D4 counterparts of these functionals and assess these in comparison. We extend our analysis beyond GMTKN55 and especially turn our attention to enzymatically catalyzed and metal–organic reactions. We find that B97M-D4 is now the second-best performing meta-generalized-gradient approximation functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies compared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(..