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arXiv · 2610.03583

CIS(2): a state-specific, size-intensive perturbative correction to configuration interaction singles

Takashi Tsuchimochi
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Abstract

We present a state-specific second-order perturbation theory based on a configuration interaction singles (CIS) reference and its generalized Fock operator. Starting from a fully internally contracted construction, we retain the complete doubles space and internally contracted triples in the first-order wave function. We consider two partitions, Canonical and Block-diagonal, with reference excitation energies given by the Fock excitation gap $ω^{(0)}$ and the CIS excitation energy $ω_{\rm CIS}$, respectively. Our analysis establishes that strict size-intensivity is preserved when the contracted-triples denominators use bare Fock gaps and the occupied--virtual Fock block is projected to remove residual spectator coupling. Based on this observation, combining Canonical triples with Block-diagonal doubles yields a size-intensive Hybrid partition. These properties are verified for water with non-interacting helium atoms. Our formulation enables $O(o^3v^2)$ cost per matrix--vector product in a semicanonical basis. On the QUEST\#1 benchmark, Canonical and Block-diagonal show opposite systematic biases, whereas Hybrid gives the best overall accuracy among the three partitions. Its mean absolute errors for singlets and triplets are 0.24 and 0.15~eV, compared with 0.28 and 0.22~eV for CIS(D). The improvement is largest for Rydberg excitations, although CIS(D) remains more accurate for valence singlets.

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Takashi Tsuchimochi. 2026-10-02. CIS(2): a state-specific, size-intensive perturbative correction to configuration interaction singles. https://arxiv.org/abs/2610.03583

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