Toward a correct treatment of core properties with local hybrid functionals

Abstract

AbstractIn local hybrid functionals (LHs), a local mixing function (LMF) determines the position‐dependent exact‐exchange admixture. We report new LHs that focus on an improvement of the LMF in the core region while retaining or partly improving upon the high accuracy in the valence region exhibited by the LH20t functional. The suggested new pt‐LMFs are based on a Padé form and modify the previously used ratio between von Weizsäcker and Kohn–Sham local kinetic energies by different powers of the density to enable flexibly improved approximations to the correct high‐density and iso‐orbital limits relevant for the innermost core region. Using TDDFT calculations for a set of K‐shell core excitations of second‐ and third‐period systems including accurate state‐of‐the‐art relativistic orbital corrections, the core part of the LMF is optimized, while the valence part is optimized as previously reported for test sets of atomization energies and reaction barriers (Haasler et al., J Chem Theory Comput 2020, 16, 5645). The LHs are completed by a calibration function that minimizes spurious nondynamical correlation effects caused by the gauge ambiguities of exchange‐energy densities, as well as by B95c meta‐GGA correlation. The resulting LH23pt functional relates to the previous LH20t functional but specifically improves upon the core region.