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.

Keywords

Hybrid functionalKinetic energyDensity functional theoryWork (physics)Range (aeronautics)Dissociation (chemistry)Statistical physicsPhysicsAtomic physicsChemistryQuantum mechanicsMaterials sciencePhysical chemistry

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Publication Info

Year
2003
Type
article
Volume
118
Issue
3
Pages
1068-1073
Citations
368
Access
Closed

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Cite This

Juanita Jaramillo, Gustavo E. Scuseria, Matthias Ernzerhof (2003). Local hybrid functionals. The Journal of Chemical Physics , 118 (3) , 1068-1073. https://doi.org/10.1063/1.1528936

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DOI
10.1063/1.1528936