EOM/Propagator ionization potentials: Extension of the excitation operator manifold

The excitation operator manifold required for the calculation of vertical IPs in the EOM/propagator formalism is extended to include products of five spin orbital field operators (refered to as the h₅ basis). Spin symmetry adaptation is used for all the operators of this manifold. Using a direct diagonalization technique introduced previously the effect of inclusion of the h₅ basis on calculated IPs is illustrated for various levels of approximation to the electron density by numerical applications to ethylene and water. The fourth-order terms thus introduced are shown to have greater magnitude than previously included third-order terms, in agreement with earlier work.