Local Hybrid Functional Applicable to Weakly and Strongly Correlated Systems.

Abstract

The recent idea (Wodyński, A.; Arbuznikov, A. V.; Kaupp M. J. Chem. Phys. 2021, 155, 144101) to augment local hybrid functionals by a strong-correlation (sc) factor obtained from the adiabatic connection in the spirit of the KP16 model has been extended and applied to generate the accurate sc-corrected local hybrid functional scLH22t. By damping small values of the ratio between nondynamical and dynamical correlation entering the correction factor, it has become possible to avoid double counting of nondynamical correlation for weakly correlated situations and thereby preserve the excellent accuracy of the underlying LH20t local hybrid for such cases almost perfectly. On the other hand, scLH22t improves substantially over LH20t in reducing fractional-spin errors (FSEs), in providing improved spin-restricted bond dissociation curves, and in treating some typical systems with multireference character. The obtained FSEs are similar to those of the KP16/B13 model and slightly larger than for B13, but performance for weakly correlated systems is better than for these two related methods, which are also difficult to use self-consistently. The recent DM21 functional based on the training of a deep neural network still performs somewhat better than scLH22t but allows no physical insights into the origins of reduced FSEs. Examination of local mixing functions (LMFs) for the corrected scLH22t and uncorrected LH20t functionals provides further insights: in weakly correlated situations, the LMF remains essentially unchanged. Strong-correlation effects manifest in a reduction of the LMF values in certain regions of space, even to the extent of producing negative LMF values. It is suggested that this is the mechanism by which also DM21, which may be viewed as a range-separated local hybrid, is able to reduce FSEs.