Geminal wavefunctions, introduced in the late 1950s, have long been recognized for their ability to compactly capture strong electron correlation. Despite their promise, they were historically overshadowed by more computationally efficient methods. Advances in both computational resources and theoretical frameworks have renewed interest in geminal-based approaches, particularly as researchers seek accurate yet tractable wavefunctions for complex electronic systems. Recent developments highlight their versatility: from serving as efficient starting points for correlated wavefunctions, to hybrid formulations that blend geminal concepts with coupled-cluster theory, to emerging applications in quantum algorithms where orbital-pairing provides a natural structure. In this mini-review, we summarize key advances in geminal wavefunction theory, with a focus on their modern resurgence, new methodological innovations, and potential directions for electronic structure theory and quantum computation.Geminal wavefunctions, introduced in the late 1950s, have long been recognized for their ability to compactly capture strong electron correlation. Despite their promise, they were historically overshadowed by more computationally efficient methods. Advances in both computational resources and theoretical frameworks have renewed interest in geminal-based approaches, particularly as researchers seek accurate yet tractable wavefunctions for complex electronic systems. Recent developments highlight their versatility: from serving as efficient starting points for correlated wavefunctions, to hybrid formulations that blend geminal concepts with coupled-cluster theory, to emerging applications in quantum algorithms where orbital-pairing provides a natural structure. In this mini-review, we summarize key advances in geminal wavefunction theory, with a focus on their modern resurgence, new methodological innovations, and potential directions for electronic structure theory and quantum computation.

arXiv:2604.16133Apr 17, 20260 citations

Correlated electronic structure theory for challenging systems

Daniel J. Taylor

May 1, 20150 citations

Theoretical studies of strongly correlated electronic systems

Hong Yao

Jan 1, 20090 citations

Hubbard Operators in the Theory of Strongly Correlated Electrons

Sergei G. Ovchinnikov, Valerii Vladimirovich Val'kov

Hubbard Model as the Simplest Model of Strong Electron Correlation Multielectron Models in X-Operators Representation General Approach to the Quasiparticle Description of Strongly Correlated Systems Unitary Transformations Method in Atomic Representation Diagram Technique in the X-Operators Representation Spectral Properties of the Anisotropic Metallic Ferromagnets Peculiarities of the de Haas-van Alphen Effect in Strongly Correlated Systems with Magnetic Polaron States The Electronic Structure of Copper Oxides in the Multiorbital p-d ModelHubbard Model as the Simplest Model of Strong Electron Correlation Multielectron Models in X-Operators Representation General Approach to the Quasiparticle Description of Strongly Correlated Systems Unitary Transformations Method in Atomic Representation Diagram Technique in the X-Operators Representation Spectral Properties of the Anisotropic Metallic Ferromagnets Peculiarities of the de Haas-van Alphen Effect in Strongly Correlated Systems with Magnetic Polaron States The Electronic Structure of Copper Oxides in the Multiorbital p-d Model

IMPERIAL COLLEGE PRESS eBooksJan 1, 200484 citations

Strong Correlation in Molecular Periodic Systems from a Variational Reduced Density Matrix Theory

Simon Ewing, David A. Mazziotti

Molecular periodic systems have the challenge of not only representing an infinite, albeit periodically repeating, molecule but also treating the strong electron correlation that emerges in such systems. Many post-Hartree-Fock methods that are efficient in moderately correlated molecules often fail to describe strongly correlated electrons and their properties in periodic systems. Here we develop and apply an electronic structure approach to periodic systems based on the variational calculation of the two-electron reduced density matrix (2-RDM). The variational 2-RDM method calculates a lower bound to the ground-state energy of a molecular periodic system without computation or storage of its many-electron wave function. The 2-RDM is constrained by $N$ -representability conditions that are necessary for it to represent at least one $N$ -electron density matrix---conditions that allow it to treat strongly correlated systems. Two periodic systems are treated to demonstrate the methodology: (i) a metallic hydrogen chain and (ii) a strongly correlated acene chain. In the hydrogen chains the 2-RDM theory describes the strongly correlated Mott metal-to-insulator transition while in acene chains it describes the emergence of polyradical character with increasing chain length. The methodology is applicable to treating strong electron correlation in more general periodic molecules and materials.Molecular periodic systems have the challenge of not only representing an infinite, albeit periodically repeating, molecule but also treating the strong electron correlation that emerges in such systems. Many post-Hartree-Fock methods that are efficient in moderately correlated molecules often fail to describe strongly correlated electrons and their properties in periodic systems. Here we develop and apply an electronic structure approach to periodic systems based on the variational calculation of the two-electron reduced density matrix (2-RDM). The variational 2-RDM method calculates a lower bound to the ground-state energy of a molecular periodic system without computation or storage of its many-electron wave function. The 2-RDM is constrained by $N$-representability conditions that are necessary for it to represent at least one $N$-electron density matrix---conditions that allow it to treat strongly correlated systems. Two periodic systems are treated to demonstrate the methodology: (i) a metallic hydrogen chain and (ii) a strongly correlated acene chain. In the hydrogen chains the 2-RDM theory describes the strongly correlated Mott metal-to-insulator transition while in acene chains it describes the emergence of polyradical character with increasing chain length. The methodology is applicable to treating strong electron correlation in more general periodic molecules and materials.

Aug 6, 20202 citations

N

-representability conditions that are necessary for it to represent at least one

N

-electron density matrix---conditions that allow it to treat strongly correlated systems. Two periodic systems are treated to demonstrate the methodology: (i) a metallic hydrogen chain and (ii) a strongly correlated acene chain. In the hydrogen chains the 2-RDM theory describes the strongly correlated Mott metal-to-insulator transition while in acene chains it describes the emergence of polyradical character with increasing chain length. The methodology is applicable to treating strong electron correlation in more general periodic molecules and materials.