title: Bridging Single- and Multireference Domains for Electron Correlation: Spin-Extended Coupled Electron Pair Approximation.
abstract: We propose a size-consistent generalization of the recently developed spin-extended configuration interaction with singles and doubles (ECISD), where a CI wave function is explicitly spin-projected. The size-consistent effect is effectively incorporated by treating quadruples within the formulation of coupled electron pair approximation. As in coupled-cluster theory, quadruple excitations are approximated by a disconnected product of double excitations. Despite its conceptual similarity to the standard single-reference and multireference analogues, such a generalization requires careful derivation, as the spin-projected CI space is nonorthogonal and overcomplete. Although our methods generally yield better results than ECISD, size-consistency is only approximately retained because the action of a symmetry-projection operator is size-inconsistent. In this work, we focus on simple models where exclusion-principle-violating terms, which eliminate undesired contributions to the correlation effects, are either completely neglected or averaged. These models possess an orbital-invariant energy functional that is to be minimized by diagonalizing an energy-shifted effective Hamiltonian within the singles and doubles manifold. This allows for a straightforward generalization of the ECISD analytical gradients needed to determine molecular properties and geometric optimization. Given the multireference nature of the spin-projected Hartree-Fock method, the proposed approaches are expected to handle static correlation, unlike single-reference analogues. We critically assess the performance of our methods using dissociation curves of molecules, singlet-triplet splitting gaps, hyperfine coupling constants, and the chromium dimer. The size-consistency and size-extensivity of the methods are also discussed.
authors.affiliation: Graduate School of Science, Technology, and Innovation, and ‡Graduate School of System Informatics, Kobe University , Kobe, Hyogo 657-0025, Japan.
authors.forename: Takashi
authors.identifier: http://orcid.org/0000-0002-6378-1268
authors.initials: T
authors.lastname: Tsuchimochi
authors.affiliation: Graduate School of Science, Technology, and Innovation, and ‡Graduate School of System Informatics, Kobe University , Kobe, Hyogo 657-0025, Japan.
authors.forename: Seiichiro
authors.initials: S
authors.lastname: Ten-No