"Beyond-zero-sum" range-separated local hybrid functional with improved dynamical correlation.

Recent work has shown that range-separated local hybrid (RSLH) functionals con- taining correction terms for strong-correlation and delocalization errors, such as ωLH23tdE, allow a remarkable paradigm change in the context of the usual zero-sum game between delocalization and static correlation errors in the development of density functional approximations. In this work we evaluate the modification of the dynamical correla- tion contribution for such sc-corrected RSLHs and how it affects performance for the large GMTKN55 data base of main-group theormochemistry, kinetics and noncova- lent interactions. Replacing B95c correlation in the previous functionals by a more flexible reoptimized B97c power-series expansion leads to substantial improvements. The ωLH25tdE scRSLH provides a GMTKN55 WTMAD-2 value of 2.64 kcal/mol in self-consistent calculations, when augmented by DFT-D4 corrections. This is the lowest for any rung 4 functional today. At the same time, ωLH25tdE retains the favor- able performance for spin-restricted bond dissociation, the removal of unphysical spin contamination in certain open-shell transition-metal complexes, and the correct long- range asymptotic potential resulting in excellent results for quasiparticle computations of ionization potentials, electron affinities, and band gaps.