Hybrid functionals with local range separation : Accurate atomization energies and reaction barrier heights

Titelangaben

Brütting, Moritz ; Bahmann, Hilke ; Kümmel, Stephan:
Hybrid functionals with local range separation : Accurate atomization energies and reaction barrier heights.
In: The Journal of Chemical Physics. Bd. 156 (2022) Heft 10 . - 104109.
ISSN 0021-9606
DOI: https://doi.org/10.1063/5.0082957

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Abstract

Range-separated hybrid approximations to the exchange–correlation density functional mix exact and semi-local exchange in a position-
dependent manner. In their conventional form, the range separation is controlled by a constant parameter. Turning this constant into a density
functional leads to a locally space-dependent range-separation function and thus a more powerful and flexible range-separation approach. In
this work, we explore the self-consistent implementation of a local range-separated hybrid, taking into account a one-electron self-interaction
correction and the behavior under uniform density scaling. We discuss different forms of the local range-separation function that depend
on the electron density, its gradient, and the kinetic energy density. For test sets of atomization energies, reaction barrier heights, and total
energies of atoms, we demonstrate that our best model is a clear improvement over common global range-separated hybrid functionals and
can compete with density functionals that contain multiple empirical parameters. Promising results for equilibrium bond lengths, harmonic
vibrational frequencies, and vertical ionization potentials further underline the potential and flexibility of our approach.