Spin-free generalized normal ordered coupled cluster

We present a spin-free, size-extensive, and numerically size-consistent coupled cluster method based on a generalized normal ordered exponential ansatz. This approach is a natural generalization of single-reference coupled cluster theory for arbitrary spin eigenfunctions. The working equations are size-extensive through the generalized normal order formalism and made spin-free with the spin-ensemble approach. Redundancies among excitations are eliminated by selecting only those excitations that project the reference function onto the first-order interacting space. Furthermore, by utilizing localized orbitals, the proposed method describes dissociation into open-shell fragments size-consistently. Numerical results on prototypical multireference systems at the singles and doubles level of theory are competitive with existing multireference approaches, yet with more compact working equations.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-04-07
DOI
https://doi.org/10.1063/5.0311996
Primary Topic
Advanced Chemical Physics Studies
Type
article
Field-Weighted Citation Impact
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article

Spin-free generalized normal ordered coupled cluster

N. L. Y. Lee, David P. Tew
The Journal of Chemical Physics
Advanced Chemical Physics Studies
article

Spin-free generalized normal ordered coupled cluster

N. L. Y. Lee, David P. Tew
article en

Abstract

We present a spin-free, size-extensive, and numerically size-consistent coupled cluster method based on a generalized normal ordered exponential ansatz. This approach is a natural generalization of single-reference coupled cluster theory for arbitrary spin eigenfunctions. The working equations are size-extensive through the generalized normal order formalism and made spin-free with the spin-ensemble approach. Redundancies among excitations are eliminated by selecting only those excitations that project the reference function onto the first-order interacting space. Furthermore, by utilizing localized orbitals, the proposed method describes dissociation into open-shell fragments size-consistently. Numerical results on prototypical multireference systems at the singles and doubles level of theory are competitive with existing multireference approaches, yet with more compact working equations.

The Journal of Chemical PhysicsVol. 164(13)
University of Oxford (GB)
Openalex Percentile: Top 18%
Advanced Chemical Physics Studies
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