Orbital optimized double-hybrid density functionals

Roberto Peverati; Martin Head-Gordon

doi:10.1063/1.4812689

Orbital optimized double-hybrid density functionals

J Chem Phys. 2013 Jul 14;139(2):024110. doi: 10.1063/1.4812689.

Authors

Roberto Peverati¹, Martin Head-Gordon

Affiliation

¹ Department of Chemistry, University of California, Berkeley, California 94720, USA.

PMID: 23862932
DOI: 10.1063/1.4812689

Abstract

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.