A CASCI-MRMP method based on Kohn—Sham orbitals

Abstract

Kohn-Sham orbitals are used in the previously proposed CASCI-MRMP scheme (a multi-reference Møller-Plesset (MRMP) method with a complete active space configuration interaction (CASCI) reference function). That is, the CASCI wave function was constructed using the Kohn-Sham orbitals and used as a reference function of the MRMP to incorporate the remaining dynamical correlation. The scheme was applied to the potential curves of the ground and low-lying excited states of N2, the potential curve of the ground state of CO, the barrier height of the H2CO → H2 + CO reaction, the valence π-π* and Rydberg excited states of benzene, and the low-lying excited states of ozone. Good agreement between the theory, experiment, and some benchmark calculations was obtained. The various orbitals which are investigated here do not give very different results. Rather, the choice of active space makes a considerable difference, and in particular the perturbation calculation is proved to be very important.