Iterative Cl general singles and doubles(ICIGSD)method for calculating the exact wave functions of the ground and excited states of molecules

摘要

The iterative configuration-interaction general singles and doubles(ICIGSD)method was applied to various closed-and open-shell electronic states of molecules within finite basis sets and was shown to give the exact results that are identical to the full CI ones.The structure of the ICIGSD is unique among the ICI formalisms,that is,the singularity problem intrinsic to atomic and molecular Hamiltonians can be avoided.The convergence of the ICIGSD method was fairly good regardless of the characters of the electronic states and the qualities of the basis sets;only several iterations were enough for obtaining microhartree accuracy.These favorable properties are attributed to the unique GSD structure.The present method was shown to be applicable to various spin states and to quasidegenerate states appearing in bond dissociation process.We have also applied the ICIGSD-CI method to calculate the excited states simultaneously.We have confirmed that the ICIGSD-CI method is accurate for calculating the excited states the symmetries of which are not only similar to but also different from that of the ground state.