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DFT-D4 Counterparts of Leading Meta-GGA and Hybrid Density Functionals for Energetics and Geometries

revised on 11.08.2020 and posted on 11.08.2020 by Asim Najibi, LARS GOERIGK

Previously, we introduced DFT-D3(BJ) variants of the B97M-V, ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Go- erigk, 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 catalysed and metal-organic reactions. We find that B97M-D4 is now the second-best performing meta-GGA functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies com- pared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(BJ) based functionals have not been thoroughly assessed for geometries and herein we close this gap by analysing geometries of noncovalently bound dimers and trimers, peptide conformers, water hexamers and transition-metal complexes. We find that several of the B97(M)- based methods—particularly the DFT-D4 versions—surpass the accuracy of previously studied methods for peptide conformer, water hexamer, and transition-metal complex geometries, making them safe-to-use, cost-efficient alternatives to the original methods. The DFT-D4 variants can be easily used with ORCA4.1 and above.


National Computational Merit Allocation Scheme


Email Address of Submitting Author


School of Chemistry, The University of Melbourne



ORCID For Submitting Author


Declaration of Conflict of Interest

There is no conflict of interest

Version Notes

These are the revised versions of both the manuscript and Supporting Information