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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 manuscript, it is demonstrated that single…

Chemical Physics · Physics 2025-06-12 Paul A. Johnson

Richardson-Gaudin (RG) states are employed as a variational wavefunction ansatz for strongly correlated isomers of H$_4$ and H$_{10}$. In each case a single RG state describes the seniority-zero sector quite well. Simple natural orbital…

Chemical Physics · Physics 2023-07-26 Paul A. Johnson , A. Eugene DePrince

Seniority-zero geminal wavefunctions are known to capture bond-breaking correlation. Among this class of wavefunctions, Richardson-Gaudin states stand out as they are eigenvectors of a model Hamiltonian. This provides a clear physical…

Chemical Physics · Physics 2022-12-14 Alexandre Faribault , Claude Dimo , Jean-David Moisset , Paul A. Johnson

Eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian, Richardson-Gaudin (RG) states, are used as a variational wavefunction Ansatz for strongly-correlated electronic systems. These states are geminal products whose coefficients…

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…

Strongly Correlated Electrons · Physics 2026-04-22 Thomas M Henderson , Guo P. Chen , Gustavo E. Scuseria

This chapter gives an overview of Richardson-Gaudin states which represent weakly correlated pairs of electrons. They are parametrized by sets of numbers obtained from non-linear equations. The best method to solve these equations is…

Chemical Physics · Physics 2023-12-15 Paul Andrew Johnson

Recently, ground state eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian, Richardson-Gaudin (RG) states, have been employed as a wavefunction ansatz for strong correlation. This wavefunction physically represents a…

Chemical Physics · Physics 2021-04-07 Paul A. Johnson , Hubert Fortin , Samuel Cloutier , Charles-Émile Fecteau

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…

Chemical Physics · Physics 2024-05-02 Paul A. Johnson

Geminal wavefunctions have been employed to model strongly-correlated electrons. These wavefunctions represent products of weakly-correlated pairs of electrons and reasonable approximations are computable with polynomial cost. In…

In this paper, we scrutinize the ability of seniority-zero wavefunction-based methods to model different types of non-covalent interactions, such as hydrogen bonds, dispersion, and mixed non-covalent interactions as well as prototypical…

Chemical Physics · Physics 2020-02-18 Filip Brzęk , Katharina Boguslawski , Paweł Tecmer , Piotr S. Żuchowski

Scalar products and density matrix elements of closed-shell pair geminal wavefunctions are evaluated directly in terms of the pair amplitudes, resulting in an analogue of Wick's theorem for fermions or bosons. This expression is in general…

Chemical Physics · Physics 2022-06-15 Jean-David Moisset , Charles-Émile Fecteau , Paul A. Johnson

Seniority is a useful way of organizing Hilbert space for strongly correlated systems. The exact zero-seniority wave function, doubly-occupied configuration interaction (DOCI), provides accurate results (given the right orbitals) for many…

Strongly Correlated Electrons · Physics 2026-02-25 Thomas M. Henderson , Guo P. Chen , Gustavo E. Scuseria

We show how to add the effects of residual electron correlation to a reference seniority-zero wavefunction by making a unitary transformation of the true electronic Hamiltonian into seniority-zero form. The transformation is treated via the…

Chemical Physics · Physics 2026-04-14 Daniel F. Calero-Osorio , Paul W. Ayers

Wavefunctions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach…

Chemical Physics · Physics 2017-01-18 Katharina Boguslawski , Paweł Tecmer

Ground state eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian are employed as a wavefunction ansatz to model strong electron correlation in quantum chemistry. This wavefunction is a product of weakly-interacting pairs of…

Model Hamiltonians are regularly derived from first-principles data to describe correlated matter. However, the standard methods for this contain a number of largely unexplored approximations. For a strongly correlated impurity model…

We introduce a set of coherent states which are associated with quantum systems governed by a trilinear boson Hamiltonian. These states are produced by the action of a nonunitary displacement operator on a reference state and can be…

Quantum Physics · Physics 2009-10-30 C. Brif

Currently, there is a growing interest in the development of a new hierarchy of methods based on the concept of seniority, which has been introduced quite recently in quantum chemistry. Despite the enormous potential of these methods, the…

Chemical Physics · Physics 2022-12-07 Bruno Senjean , Saad Yalouz , Naoki Nakatani , Emmanuel Fromager

Slater determinants underpin most electronic structure methods, but orbital-based approaches often struggle to describe strong correlation efficiently. Geminal-based theories, by contrast, naturally capture static correlation in…

Eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian have recently been employed as a variational wavefunction ansatz in quantum chemistry. This wavefunction is a mean-field of pairs of electrons (geminals). In this…

Chemical Physics · Physics 2020-08-31 Charles-Émile Fecteau , Hubert Fortin , Samuel Cloutier , Paul A. Johnson
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