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

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.

Automated summary

This work explores the self-consistent implementation of a local range-separated hybrid and discusses different forms of the local range-separation function. Experimental results demonstrate that this approach is significantly better than common global range-separated hybrid functionals in terms of atomization energy, reaction barrier height, and total energy of atoms. Furthermore, promising results are obtained for equilibrium bond lengths, harmonic vibrational frequencies, and vertical ionization potentials, highlighting the potential and flexibility of this approach.