EOMCC over excited state Hartree-Fock solutions (ESHF-EOMCC): An efficient approach for the entire ground state potential energy curves of higher-order bonds

Abstract

The equation-of-motion coupled cluster (EOMCC) method based on the excited state Hartree-Fock (ESHF) solutions is shown to be appropriate for computing the entire ground state potential energy curves of strongly correlated higher-order bonds. The new approach is best illustrated for the homolytic dissociation of higher-order bonds in molecules. The required multireference character of the true ground state wavefunction is introduced through the linear excitation operator of the EOMCC method. Even at the singles and doubles level of cluster excitation truncation, the nonparallelity error of the ground state potential energy curve from the ESHF based EOMCC method is small.