Using the charge stabilization technique in the double ionization potential equation-of-motion calculations with dianion references

T. Kus and A. I. Krylov
J. Chem. Phys. 135, 084109 (2011)

The charge stabilization method is applied to double ionization potential equation-of-motion (EOM-DIP) calculations to stabilize unstable dianion reference functions. The auto-ionizing character of the dianionic reference states spoils the numeric performance of EOM-DIP limiting applications of this method. We demonstrate that reliable EOM-DIP excitation energies can be computed using a stabilized resonance wave function instead of the lowest energy solution corresponding to the neutral + free electron(s) state of the system. The details of charge stabilization procedure are discussed and illustrated by examples. Our benchmark calculations of the singlet-triplet energy gaps in several diradicals show a remarkable improvement of the EOM-DIP accuracy in problematic cases.

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