Second-order perturbation theory using correlated orbitals. II. A coupled MCSCF perturbation strategy for electronic spectra and its applications to ethylene, formaldehyde and vinylidene Original Research Article

In this second paper, the philosophy of coupling multiconfigurational variational wave functions to perturbation treatments (MC/P methodology) is extended to the calculation of electronic spectra. The corresponding methodology is presented with emphasis on its flexibility and an overview of other available approaches is given. The contracted MC/P scheme is then applied to ethylene H2CCH2, formaldehyde H2CO vinylidene H2CC. It is shown that combining well-designed averaged zeroth-order MCSCF wave functions to a barycentric Møller-Plesset (BMP) partition of the electronic Hamiltonian provides accurate spectra, contrary to Epstein-Nesbet partitions. The MC/BMP transition energies compare with experimental data within a few hundreds of cm−1. These results have been obtained using a polarized double-zeta quality basis set augmented by a set of semi-diffuse functions (6–31 + G∗) and by an extra set of diffuse orbitals to account for Rydberg states. Since non-dynamic correlations effects that are important for a proper description of the manifold of the excited states of interest are included in the MCSCF zeroth-order space will all remaining correlation effects (non-dynamic and dynamic) are treated at the perturbation level, the present study lets anticipate applications of the MC/P methodology to medium size systems without much computational trouble.