Global Hybrids from the Semiclassical Atom Theory Satisfying the Local Density Linear Response

Eduardo Fabiano (1, 2) , Lucian A. Constantin (1) , Pietro Cortona (3) , Fabio Della Sala (1, 2)

1 Center for Biomolecular Nanotechnologie
2 CNR NANO - Istituto Nanoscienze [Modena]
3 SPMS - Laboratoire Structures, Propriétés et Modélisation des solides

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.

Domaines: Science des matériaux [cond-mat.mtrl-sci]

Eduardo Fabiano, Lucian A. Constantin, Pietro Cortona, Fabio Della Sala. Global Hybrids from the Semiclassical Atom Theory Satisfying the Local Density Linear Response. Journal of Chemical Theory and Computation, 2015, 11, pp.122-131. ⟨10.1021/ct500902p⟩. ⟨hal-01258413⟩