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arXiv:2506.09379 · The Journal of Chemical Physics

Richardson–Gaudin states of non-zero seniority. II. Single-reference treatment of strong correlation

Paul A. Johnson

Published Aug 22, 2025• 4 citations
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Abstract

Strongly correlated systems are well described as a configuration interaction of Slater determinants classified by their number of unpaired electrons. This treatment is, however, unfeasible. In this paper, it is demonstrated that single reference methods built from Richardson-Gaudin states yield comparable results at polynomial cost.
DOI
10.1063/5.0284864

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Single reference treatment of strongly correlated H4_44​ and H10_{10}10​ isomers with Richardson-Gaudin states
Richardson-Gaudin (RG) states are employed as a variational wavefunction ansatz for strongly correlated isomers of H4_44​ and H10_{10}10​. In each case a single RG state describes the seniority-zero sector quite well. Simple natural orbital functionals offer a cheap and reasonable approximation of the outstanding weak correlation in the seniority-zero sector, while systematic improvement is achieved by performing a configuration interaction (CI) in terms of RG states. Other pair theories (e.g. generalized valence bond and pair-coupled-cluster doubles) can provide a good description of many of the geometries considered, but, at short distances, the wavefunctions for the 2D and 3D structures of H10_{10}10​ take the form of an RG state that cannot be described by these other theories.
Richardson-Gaudin states provide a basis of the Hilbert space for strongly correlated electrons. In this study, optimal expressions for the transition density matrix elements between Richardson-Gaudin states are obtained with a cost comparable with the corresponding reduced density matrix elements. Analogues of the Slater-Condon rules are identified based on the number of near-zero singular values of the RG state overlap matrix. Finally, a perturbative approach is shown to be close in quality to a configuration interaction of Richardson-Gaudin states while being feasible to compute.
Standard approaches to approximating solutions to the Schroedinger equation rely upon the assumption that there is a single dominant electronic configuration with a small number of low-lying excited states. As such, they are referred to as single reference approaches and are accurate only when the band gap is small in comparison with the inter-electronic repulsion of the valence electrons. Systems for which this is the case are weakly-correlated. If the inter-electronic repulsion larger than the band gap, then a single electronic reference is not an appropriate ansatz for the physical wavefunction. As the strength of the interaction is increased many Slater determinants become near-degenerate, each providing non-negligible contributions. Such systems are strongly-correlated. The goal of the thesis was to employ wavefunctions which are: non-trivial, tractable, size-consistent and extensive, and not given in an active space. We have outlined approaches based on wavefunction forms more suited to describe strong correlation. Built on the Lie algebra su(2), our first trial wavefunction was the Bethe ansatz solution to the reduced BCS Hamiltonian derived by Richardson. This wavefunction is expressed as a product of quasi-particles each parametrized in terms of quasi-momenta. Consistency among the quasi-momenta is ensured by a set of non-linear equations to be solved numerically. This approach is feasible in both variational and projected flavours. We next considered a wavefunction of the same form without requiring it to be an eigenvector of the reduced BCS Hamiltonian. A variational approach in this case is only feasible provided there are two equivalent descriptions in terms of particles and holes. In any case, a bivariational principle and a projected approach are both feasible. Also based on su(2), there is AP1roG (coupled cluster pair doubles). Open-shell singlets and triplets were constructed with the Lie algebras sp(N) and so(4N). The resulting formulae appear to be infeasible unless it is possible to efficiently compute generalizations of determinants to three-dimensional objects. Treating each spatial orbital individually, all four possible occupations close the Lie superalgebra gl(2|2).
Integrable systems take a special niche in quantum many-body systems. Due to the underlying algebraic structure, it is possible to capture all the quantum correlations exactly within a Bethe Ansatz wavefunction at a favourably scaling computational cost. Richardson [1] and Gaudin [2] have shown that the reduced Bardeen-Cooper-Schrieffer (BCS) Hamiltonian of superconductivity [3] is integrable and that the Bethe Ansatz state corresponds to a product wave function of generalized Cooper pairs [4]. In this formulation, the Bethe ansatz state is equivalent to a non-orthogonal geminal, which is widely used in quantum chemistry to describe electron pair correlations in atoms and molecules [5]. Inspired by Richardson-Gaudin integrable systems, it is possible to construct classes of non-orthogonal geminals, allowing for an accurate description of realistic and non-integrable strongly correlated atoms and molecules, while retaining the favorable computational scaling [6, 7]. In this contribution, I will discuss Richardson-Gaudin integrability and why it is useful for strongly correlated systems.
Zero-seniority methods have shown great promise for the description of strongly-correlated electronic systems. Other seniority sectors have been much less explored, and in particular the maximal seniority sector and zero seniority have the same underlying algebraic structure. We introduce a seniority eigenstate configuration interaction in which the wave function is constrained to have good fixed local seniority for each paired orbital, by which we mean we partition orbitals into a pairing set with seniority zero, and a spin set with seniority one. We show how to build the effective Hamiltonian for this ansatz, and demonstrate that high-seniority wave functions have unexpectedly excellent accuracy for strongly-correlated fermionic systems, with accuracy competitive with or better than seniority zero for the Hubbard model and for the dissociation of the nitrogen molecule.