Away from generalized gradient approximation: orbital-dependent exchange-correlation functionals.

Abstract

The local-density approximation of density functional theory (DFT) is remarkably accurate, for instance, for geometries and frequencies, and the generalized gradient approximations have also made bond energies quite reliable. Sometimes, however, one meets with failure in individual cases. One of the possible routes towards better functionals would be the incorporation of orbital dependence (which is an implicit density dependency) in the functionals. We discuss this approach both for energies and for response properties. One possibility is the use of the Hartree-Fock-type exchange energy expression as orbital-dependent functional. We will argue that in spite of the increasing popularity of this approach, it does not offer any advantage over Hartree-Fock for energies. We will advocate not to apply the separation of exchange and correlation, which is so ingrained in quantum chemistry, but to model both simultaneously. For response properties the energies and shapes of the virtual orbitals are crucial. We will discuss the benefits that Kohn-Sham potentials can offer which are derived from either an orbital-dependent energy functional, including the exact-exchange functional, or which can be obtained directly as orbital-dependent functional. We highlight the similarity of the Hartree-Fock and Kohn-Sham occupied orbitals and orbital energies, and the essentially different meanings the virtual orbitals and orbital energies have in these two models. We will show that these differences are beneficial for DFT in the case of localized excitations (in a small molecule or in a fragment), but are detrimental for charge-transfer excitations. Again, orbital dependency, in this case in the exchange-correlation kernel, offers a solution.