Local hybrid functionals

Abstract

We present a novel approach for constructing hybrid functionals by using a local mix of regular density functional theory (DFT) exchange and exact Hartree–Fock (HF) exchange. This local hybrid approach is computationally feasible for a wide range of molecules. In this work, the local mix of HF and DFT exchange is driven by the ratio of τW=|∇ρ|2/8ρ, the Weizsäcker kinetic energy density, with τ, the exact kinetic energy density. This particular choice of local mix yields 100% of exact exchange in one-electron regions. Dissociation energy curves, binding energies, and equilibrium geometries for two-center, three-electron symmetric radical cations can be modeled accurately using this scheme. We also report encouraging results for reaction energy barriers, and somewhat disappointing atomization energies for the small G2 set.