Papers
arxiv:2610.03583

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

Published on Oct 2
Authors:

Abstract

State-specific second-order perturbation theory using a CIS reference with fully contracted doubles and triples achieves size-intensive hybrid partitions and improves excitation energy accuracy, especially for Rydberg states.

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.

Community

Sign up or log in to comment

Get this paper in your agent:

hf papers read 2610.03583
Don't have the latest CLI?
curl -LsSf https://hf.co/cli/install.sh | bash

Models citing this paper 0

No model linking this paper

Cite arxiv.org/abs/2610.03583 in a model README.md to link it from this page.

Datasets citing this paper 0

No dataset linking this paper

Cite arxiv.org/abs/2610.03583 in a dataset README.md to link it from this page.

Spaces citing this paper 0

No Space linking this paper

Cite arxiv.org/abs/2610.03583 in a Space README.md to link it from this page.

Collections including this paper 0

No Collection including this paper

Add this paper to a collection to link it from this page.