How accurate can Kohn-Sham density functional be for both main-group and transition metal reactions.

Abstract

Achieving chemical accuracy in describing reactions involving both main-group elements and transition metals poses a substantial challenge for density functional approximations (DFAs), primarily due to the significantly different behaviors for electrons moving in the s,p-orbitals or in the d,f-orbitals. MOR41, a representative dataset of transition metal chemistry, has highlighted the PWPB95-D3(BJ) functional, a B2PLYP-type doubly hybrid (bDH) approximation equipped with an empirical dispersion correction, as the leading functional thus far (Dohm et al., J Chem Theory Comput 2018;14: 2596-2608). However, this functional is not among the top bDH methods for main-group chemistry (Goerigk et al., Phys Chem Chem Phys. 2017;19: 32184). Conversely, bDH methods such as DSD-BLYP-D3, proficient in main-group chemistry, often falter for transition metal chemistry. Herein, taking advantage of the home-made Rust-based Electronic-Structure Toolkits, we examine a suite of XYG3-type doubly hybrid (xDH) methods. We confirm that the trade-off in descriptive accuracy between main-group and transition metal systems persists within the realm of perturbation theory (PT2)-based xDH methods. Notably, however, our study ushers in a pivotal advance with the recently proposed renormalized xDH method, R-xDH7-SCC15. This method not only distinguishes itself among the elite methods for main-group chemistry, but also achieves an unprecedented accuracy for the MOR41 dataset, outperforming all other reported DFAs. The efficacy of R-xDH7-SCC15 stems from the successful integration of a renormalized PT2 correlation model (rPT2) and a machine-learning strong-correlation correction (SCC15), marking a significant step forward in the realm of computational chemistry.