A short-range gradient-corrected density functional in long-range coupled-cluster calculations for rare gas dimers

Abstract

A previously proposed scheme for coupling short-range (sr) density functionals with wavefunction-based long-range (lr) ab initio methods has been extended by (a) developing a new gradient-corrected sr functional of the Perdew–Burke–Ernzerhof (PBE) type and (b) introducing coupled-cluster (CC) approaches (CC with single and double excitations (CCSD), and with additional perturbative triples (CCSD(T))) at the ab initio side. The results show that mixing-in of lr-ab initio correlation helps to remove deficiencies of currently used density functionals for the treatment of van-der-Waals interactions. Compared to full ab initio calculations, the basis set dependence is weaker so that the accuracy of the mixed results surpasses that of the ab initio ones for basis sets of triple-zeta quality.