Full CI benchmark calculations for several states of the same symmetry

Abstract

Full CI (FCI) wave functions are used to compute energies for several electronic states of the same symmetry for SiH2, CH2, and CH+2. It is found that CASSCF/multireference CI (MRCI) wave functions yield results very similar to FCI, irrespective of whether the CASSCF MOs are optimized independently for each state or using an average of the CASSCF energies for all desired states. The ionization potentials (IPs) and excitation energies obtained from the FCI calculations should help calibrate methods such as Green’s function approaches, equations of motion and propagator methods, and cluster expansions, in which energy differences are computed directly.