Exact Generalized Kohn-Sham Theory for Hybrid Functionals

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Hybrid functionals have proven to be of immense practical value in density functional theory calculations. While they are often thought to be a heuristic construct, it has been established that this is in fact not the case. Here, we present a rigorous and formally exact generalized Kohn-Sham (GKS) density functional theory of hybrid functionals, in which exact remainder exchange-correlation potentials combine with a fraction of Fock exchange to produce the correct ground state density. Specifically, we generalize the well-known adiabatic con- nection theorem to the case of exact hybrid functional theory and use it to provide a rigorous distinction between multiplicative exchange and correlation components. We examine the exact theory by inverting reference electron densities to obtain exact GKS potentials for hybrid functionals, showing that an equivalent description of the many-electron problem is obtained with any arbitrary global fraction of Fock exchange. We establish the dependence of these exact components on the fraction of Fock exchange and use the observed trends to shed new light on the results of approximate hybrid functional calculations.

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CC BY-NC-ND 4.0