A double-hybrid density functional based on good local physics with outstanding performance on the GMTKN55 database

In two recent papers [A. D. Becke, J. Chem. Phys. 156, 214101 (2022) and A. D. Becke, J. Chem. Phys. 157, 234102 (2022)], we compared two Kohn-Sham density functionals based on physical modeling and theory with the best density-functional power-series fits in the literature. The best error statistics reported to date for a hybrid functional on the general main-group thermochemistry, kinetics, and noncovalent interactions (GMTKN55) chemical database of Goerigk et al. [Phys. Chem. Chem. Phys. 19, 32184 (2017)] were obtained. In the present work, additional second-order perturbation-theory terms are considered. The result is a 12-parameter double-hybrid density functional with the lowest GMTKN55 WTMAD2 weighted total mean absolute deviation error (1.76 kcal/mol) yet seen for any hybrid or double-hybrid density-functional approximation. We call it DH23.

Automated summary

In two recent papers, we compared two Kohn-Sham density functionals based on physical modeling and theory with the best density-functional power-series fits in the literature. The best error statistics reported so far for a hybrid functional on the GMTKN55 chemical database were obtained. In this work, additional second-order perturbation-theory terms are considered, resulting in a 12-parameter double-hybrid density functional with the lowest GMTKN55 WTMAD2 error yet seen.