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

eigenvaluesHilbert spaceelectronic structure calculationscoupled cluster method

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) Molecular physics (81V55) Many-body theory; quantum Hall effect (81V70) Applications to the sciences (65Z05)

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.

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Cited in

(1)

• Coupled Cluster Theory: Toward an Algebraic Geometry Formulation

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