Generalizing the bra state in the symmetry-adapted cluster singles and doubles method and the second-order perturbation correction

Abstract

We present a procedure to overcome the quasi-degeneracy problem in the CCSD and SACSD methods. A multi-configuration bra state in the SACSD equations (MRbra-SACSD equation) together with a second-order perturbation correction gives quantitatively correct potential curves for bond dissociations. The benchmark results for HF, F 2, and H 2O show that the perturbative triple correction reduces the deviations from Full-CI energies to within 3 mHartree (1.9 kcal/mol). Within the benchmark calculations, the results of the present method are comparable with the recent post-CCSD corrections, the CR-CCSD(T) and CCSD(2) T methods, and are slightly less accurate than the CR-CC(2,3) method.