Analysis of the single reference coupled cluster method for electronic structure calculations: the full-coupled cluster equations

DOI10.1007/S00211-023-01371-XMaRDI QIDQ6093391zbMATH OpenOpenAlexFDO

Authors

Publication date 6 October 2023

Published in Numerische Mathematik (Search for Journal in Brave)

Copyright license Creative Commons Attribution 4.0 International

Full work available at URL https://arxiv.org/abs/2212.12788

zbMATH Keywords

coupled cluster method eigenvalues electronic structure calculations Hilbert space

Mathematics Subject Classification ID

Numerical methods for eigenvalue problems for boundary value problems involving PDEs (65N25) Finite element, Rayleigh-Ritz and Galerkin methods for boundary value problems involving PDEs (65N30) Applications to the sciences (65Z05) Molecular physics (81V55) Many-body theory; quantum Hall effect (81V70)

Abstract: The central problem in electronic structure theory is the computation of the eigenvalues of the electronic Hamiltonian -- an unbounded, self-adjoint operator acting on a Hilbert space of antisymmetric functions. Coupled cluster (CC) methods, which are based on a non-linear parameterisation of the sought-after eigenfunction and result in non-linear systems of equations, are the method of choice for high accuracy quantum chemical simulations but their numerical analysis is underdeveloped. The existing numerical analysis relies on a local, strong monotonicity property of the CC function that is valid only in a perturbative regime, i.e., when the sought-after ground state CC solution is sufficiently close to zero. In this article, we introduce a new well-posedness analysis for the single reference coupled cluster method based on the invertibility of the CC derivative. Under the minimal assumption that the sought-after eigenfunction is intermediately normalisable and the associated eigenvalue is isolated and non-degenerate, we prove that the continuous (infinite-dimensional) CC equations are always locally well-posed. Under the same minimal assumptions and provided that the discretisation is fine enough, we prove that the discrete Full-CC equations are locally well-posed, and we derive residual-based error estimates with guaranteed positive constants. Preliminary numerical experiments indicate that the constants that appear in our estimates are a significant improvement over those obtained from the local monotonicity approach.

Review text

Computational quantum chemistry is by now widely regarded as one of the central pillars of modern chemistry, as evidenced by the award of two Nobel prizes. The goal of quantum chemistry is to obtain a quantitative description of the behaviour of matter at the atomic scale, where matter is viewed as a collection of nuclei and electrons. In the so-called non-relativistic Born-Oppenheimer setting, the nuclei of the molecule under study are treated as clamped, point-like particles, and the aim is to describe the evolution of the electrons in the effective electrostatic potential generated by the static configuration of positively charged nuclei, this field of study being known as electronic structure theory. The behaviour of the electrons in this situation is governed by the spectrum of the so-called electronic Hamiltonian -- a semi-unbounded, self-adjoint operator acting on an \(L^2\)-type Hilbert space of antisymmetric functions. The primary difficulty in the numerical computation of the lowest eigenvalue of the electronic Hamiltonian is the extremely high-dimensionality of the underlying Hilbert space. For a system containing N electrons, the sought-after ground state of the electronic Hamiltonian depends on 3N spatial variables. The central problem in electronic structure theory is the computation of the eigenvalues of the electronic Hamiltonian -- a semi-unbounded, self-adjoint operator acting on an \(L^2\)-type Hilbert space of antisymmetric functions. Coupled cluster (CC) methods, based on a non-linear parameterisation of the sought-after eigenfunction that result in non-linear systems of equations, are the method of choice for high-accuracy quantum chemical simulations. The existing numerical analysis of coupled cluster methods relies on a local, strong monotonicity property of the CC function that is valid only in a perturbative regime, i.e., when the sought-after ground state CC solution is sufficiently close to zero. In this article, the authors introduce a new well-posedness analysis for the single reference coupled cluster method based on the invertibility of the CC derivative. Under the minimal assumption that the sought-after eigenfunction is intermediately normalisable and the associated eigenvalue is isolated and non-degenerate, they prove that the continuous (infinite-dimensional) CC equations are always locally well-posed. Under the same minimal assumptions and provided that the discretisation is fine enough, they also prove that the discrete Full-CC equations are locally well-posed, and then derive residual-based error estimates with guaranteed positive constants. The authors present results of numerical experiments that indicate that the constants that appear in their estimates are a significant improvement over those obtained from the local monotonicity approach.

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