Chemical accuracy with σ-functionals for the Kohn-Sham correlation energy optimized for different input orbitals and eigenvalues.

Abstract

Recently, a new type of orbital-dependent functional for the Kohn-Sham (KS) correlation energy, σ-functionals, was introduced. Technically, σ-functionals are closely related to the well-known direct random phase approximation (dRPA). Within the dRPA, a function of the eigenvalues σ of the frequency-dependent KS response function is integrated over purely imaginary frequencies. In σ-functionals, this function is replaced by one that is optimized with respect to reference sets of atomization, reaction, transition state, and non-covalent interaction energies. The previously introduced σ-functional uses input orbitals and eigenvalues from KS calculations with the generalized gradient approximation (GGA) exchange-correlation functional of Perdew, Burke, and Ernzerhof (PBE). Here, σ-functionals using input orbitals and eigenvalues from the meta-GGA TPSS and the hybrid-functionals PBE0 and B3LYP are presented and tested. The number of reference sets taken into account in the optimization of the σ-functionals is larger than in the first PBE based σ-functional and includes sets with 3d-transition metal compounds. Therefore, also a reparameterized PBE based σ-functional is introduced. The σ-functionals based on PBE0 and B3LYP orbitals and eigenvalues reach chemical accuracy for main group chemistry. For the 10966 reactions from the highly accurate W4-11RE reference set, the B3LYP based σ-functional exhibits a mean average deviation of 1.03 kcal/molcompared to 1.08 kcal/molfor the coupled cluster singles doubles perturbative triples method if the same valence quadruple zeta basis set is used. For 3d-transition metal chemistry, accuracies of about 2 kcal/molare reached. The computational effort for the post-self-consistent evaluation of the σ-functional is lower than that of a preceding PBE0 or B3LYP calculation for typical systems.