Quasidegenerate second-order perturbation corrections to single-excitation configuration interaction

A family of quasidegenerate second-order perturbation theories that correct excitation energies from single-excitation configuration interaction (CIS) are introduced which generalize the earlier non-degenerate second-order method, CIS(D). The new methods are termed CIS(Dn), where n ranges from 0 to ∞, according to the number of terms retained in a doubles denominator expansion. Truncation at either n = 0 or n = 1 yields methods which involve the diagonalization of a dressed singles-only response matrix, where the dressing is state-independent. Hence CIS(D0) and CIS(D1) can be implemented efficiently using semidirect methods, which are discussed. Test calculations on formaldehyde, ethylene, chlorine nitrate, styrene, benzaldehyde, and chalcone are presented to assess the performance of these methods. CIS(D0) and CIS(D1) both show significant improvements relative to CIS(D) in cases of near-degeneracy.

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