Orbital optimized double-hybrid density functionals.

This paper advocates development of a new class of double-hybrid (DH) density functionals where the energy is fully orbital optimized (OO) in presence of all correlation, rather than using a final non-iterative second order perturbative correction. The resulting OO-DH functionals resolve a number of artifacts associated with conventional DH functionals, such as first derivative discontinuities. To illustrate the possibilities, two non-empirical OO-DH functionals are obtained from existing DH functionals based on PBE: OO-PBE0-DH and OO-PBE0-2. Both functionals share the same functional form, with parameters determined on the basis of different physical considerations. The new functionals are tested on a variety of bonded, non-bonded and symmetry-breaking problems.