title: Global hybrids from the semiclassical atom theory satisfying the local density linear response.
abstract: We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 2011, 106, 186406] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetic and structural testing, including thermochemistry and geometry, transition metal complexes, noncovalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semiempirical dispersion corrections are also provided.
authors.affiliation: National Nanotechnology Laboratory (NNL), Istituto Nanoscienze-CNR , Via per Arnesano 16, I-73100 Lecce, Italy.|Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia , Via Barsanti, I-73010 Arnesano, Italy.
authors.forename: Eduardo
authors.initials: E
authors.lastname: Fabiano
authors.affiliation: Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia , Via Barsanti, I-73010 Arnesano, Italy.
authors.forename: Lucian A
authors.initials: LA
authors.lastname: Constantin
authors.affiliation: Laboratoire Structures, Propriétés et Modélisation des Solides, CNRS UMR 8580, École Centrale Paris, Grand Voie des Vignes , F-92295 Châtenay-Malabry, France.
authors.forename: Pietro
authors.initials: P
authors.lastname: Cortona
authors.affiliation: National Nanotechnology Laboratory (NNL), Istituto Nanoscienze-CNR , Via per Arnesano 16, I-73100 Lecce, Italy.|Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia , Via Barsanti, I-73010 Arnesano, Italy.
authors.forename: Fabio
authors.initials: F
authors.lastname: Della Sala
mesh_terms: D008670:Metals / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D008670:Metals