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New ideas to reduce the computational complexity of non- orthogonal geminal methods for strongly-correlated electronic systems

Patrick Cassam‐Chenaï

Published Feb 4, 2018• 1 citation
OpenAlex

Abstract

The Lewis electron-pair picture pervades all of chemistry and a substantialdomain of materials science. “Geminals” are electron-pair quantum states whichare used to express approximate solutions of the Schrödinger equation of polyelec-tronic systems. In quantum chemistry, geminal-based methods are potentially moreeffective than the traditional ones based on the orbital picture: electrons occupyorbitals and experience only the average effect of each other. This is especially truefor strongly correlated-systems. However, the computational cost of using arbitrarygeminal wave functions is non-polynomial in the system size.It is therefore an important challenge to find additional constraints on geminalmodels which preserve the accuracy of the wavefunction description while reducingthe calculations to polynomial cost. The Ayers’ group at Mc Master has developedone such successful geminal model called AP1roG because the wavefunction is anantisymmetric product of geminals with one distinct reference orbital occupied ineach geminal [1]. This ansatz relaxes the so-called “strong-orthogonality” constraintbetween geminals. The latter makes wavefunction matrix element computationsvery easy but appears too drastic from the physical point of view, since the geminalelectron pairs are then distinguishable.We have followed a different path to relax the strong-orthogonality constraint. Wehave defined the geometrical concept of n-orthogonality [2] which can be viewed asa graded indistinguishability measure for electronic states: 1-orthogonality coincideswith strong orthogonality, the larger n the less distinguishable the n-orthogonal elec-tronic states will be. We have studied geminal models constrained by n-orthogonalityrelations for different values of n, imposed to different combinations of geminal prod-uct states [3]. However, in this work the scaling of matrix element computations wasstill unsatisfactory. We will present new ideas developed since then to remedy thisproblem.References[1] P. A Limacher, P. W. Ayers, P. A. Johnson, S. De Baerdemacker, D. Van Neck and P. Bultinck, J. of Chem. Theory and Computation 9, 1394-1401 (2013).[2] P. Cassam-Chenaı̈, Phys. Rev. A77, 032103 (2008).[3] P. Cassam-Chenaı̈, V. Rassolov, Chem. Phys. Lett. 487, 147-152 (2010).

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The Lewis electron-pair picture pervades all of chemistry and a substantialdomain of materials science. “Geminals” are electron-pair quantum states whichare used to express approximate solutions of the Schrödinger equation of polyelec-tronic systems. In quantum chemistry, geminal-based methods are potentially moreeffective than the traditional ones based on the orbital picture: electrons occupyorbitals and experience only the average effect of each other. This is especially truefor strongly correlated-systems. However, the computational cost of using arbitrarygeminal wave functions is non-polynomial in the system size.It is therefore an important challenge to find additional constraints on geminalmodels which preserve the accuracy of the wavefunction description while reducingthe calculations to polynomial cost. The Ayers’ group at Mc Master has developedone such successful geminal model called AP1roG because the wavefunction is anantisymmetric product of geminals with one distinct reference orbital occupied ineach geminal [1]. This ansatz relaxes the so-called “strong-orthogonality” constraintbetween geminals. The latter makes wavefunction matrix element computationsvery easy but appears too drastic from the physical point of view, since the geminalelectron pairs are then distinguishable.We have followed a different path to relax the strong-orthogonality constraint. Wehave defined the geometrical concept of n-orthogonality [2] which can be viewed asa graded indistinguishability measure for electronic states: 1-orthogonality coincideswith strong orthogonality, the larger n the less distinguishable the n-orthogonal elec-tronic states will be. We have studied geminal models constrained by n-orthogonalityrelations for different values of n, imposed to different combinations of geminal prod-uct states [3]. However, in this work the scaling of matrix element computations wasstill unsatisfactory. We will present new ideas developed since then to remedy thisproblem.References[1] P. A Limacher, P. W. Ayers, P. A. Johnson, S. De Baerdemacker, D. Van Neck and P. Bultinck, J. of Chem. Theory and Computation 9, 1394-1401 (2013).[2] P. Cassam-Chenaı̈, Phys. Rev. A77, 032103 (2008).[3] P. Cassam-Chenaı̈, V. Rassolov, Chem. Phys. Lett. 487, 147-152 (2010).
The energy of a molecule is not the sum of the energies of its atomic components. Our aim is to compute an accurate approximation of this quantity based on an electron pair model, that is to say by using an antisymmetric product of two-electron wave functions, called “geminals”. In this model, the total wave function can also be described in a more practical way, by a set of matrices, one for each geminal. However, without further restrictions, such a model has a factorial computational complexity with the number of electrons and its applicability is therefore limited to small systems.We have introduced generalized orthogonality constraints between geminals to reduce the computational effort to a polynomial cost, without sacrificing the indistinguishability of the electrons. In other words, the electron pairs corresponding to the geminals are not fully distinguishable, so that our model remains complex, in the sense that geminal products have still to be antisymmetrized according to the Pauli principle to form bona fide electronic wave functions.Our geometrical constraints translate, in terms of geminal matrices, into simple equations involving the traces of products of these matrices. In the simplest non-trivial model, a set of solutions is given by block-diagonal matrices where each block is of size 2x2 and consists of a Pauli matrix or the Identity, multiplied by a complex parameter to be optimized. With this simplified ansatz for geminals, the number of terms in the calculation of the matrix elements of quantum observables is considerably reduced.
We present a new geminal product wave function Ansatz where the geminals are not constrained to be strongly orthogonal or to be of seniority-zero. Instead, we introduce weaker orthogonality constraints between geminals that significantly lower the computational effort without sacrificing the indistinguishability of the electrons. That is to say, the electron pairs corresponding to the geminals are not fully distinguishable, and their product has yet to be antisymmetrized according to the Pauli principle to form a bona fide electronic wave function. Our geometrical constraints translate into simple equations involving the traces of products of our geminal matrices. In the simplest non-trivial model, a set of solutions is given by block-diagonal matrices where each block is 2 × 2 and consists of either a Pauli matrix or a normalized diagonal matrix multiplied by a complex parameter to be optimized. With this simplified Ansatz for geminals, the number of terms in the calculation of the matrix elements of quantum observables is considerably reduced. A proof of principle is reported and confirms that the Ansatz is more accurate than strongly orthogonal geminal products while remaining computationally affordable.
Strong orthogonality is an important constraint placed on geminal wavefunctions in order to make variational minimization tractable. However, strong orthogonality prevents certain, possibly important, excited configurations from contributing to the ground state description of chemical systems. The presented method lifts strong orthogonality constraint from geminal wavefunction by computing a perturbative-like correction to each geminal independently from the corrections to all other geminals. The method is applied to the Singlet-type Strongly orthogonal Geminals variant of the geminal wavefunction. Comparisons of this new SS(p)G method are made to the non-orthogonal AP1roG and the unconstrained Geminal Mean-Field Configuration Interaction method using small atomic and molecular systems. The correction is also compared to Density Matrix Renormalization Group calculations performed on long polyene chains in order to assess its scalability and applicability to large strongly correlated systems. The results of these comparisons demonstrate that although the perturbative correction is small, it may be a necessary first step in the systematic improvement of any strongly orthogonal geminal method.
Electron pairs have an illustrious history in chemistry, from powerful concepts to understanding structural stability and reactive changes to the promise of serving as building blocks of quantitative descriptions of the electronic structure of complex molecules and materials. However, traditionally, two-electron wavefunctions (geminals) have not enjoyed the popularity and widespread use of the more standard single-particle methods. This has changed recently, with a renewed interest in the development of geminal wavefunctions as an alternative to describing strongly correlated phenomena. Hence, there is a need to find geminal methods that are accurate, computationally tractable, and do not demand significant input from the user (particularly via cumbersome and often ill-behaved orbital optimization steps). Here, we propose new families of geminal wavefunctions inspired by the pair coupled cluster doubles ansatz. We present a new hierarchy of two-electron wavefunctions that extends the one-reference orbital idea to other geminals. Moreover, we show how to incorporate single-like excitations in this framework without leaving the quasiparticle picture. We explore the role of imposing seniority restrictions on these wavefunctions and benchmark these new methods on model strongly correlated systems.
In this review, we discuss the recent progress in developing geminal-based theories for challenging problems in quantum chemistry. Specifically, we focus on the antisymmetrized geminal power, generalized valence bond, antisymmetrized product of strongly orthogonal geminals, singlet-type orthogonal geminals, the antisymmetric product of 1-reference orbital geminal, also known as the pair coupled cluster doubles ansatz, and geminals constructed from Richardson-Gaudin states. Furthermore, we review various corrections to account for the missing dynamical correlation effects in geminal models and possible extensions to target electronically excited states and open-shell species. Finally, we discuss some numerical examples and present-day challenges for geminal-based models, including a quantitative and qualitative analysis of wave functions, and software availability.
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.