Finite-size effects in periodic coupled cluster calculations

Fuente: arXiv
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Auteurs principaux: Xing, Xin, Lin, Lin
Format: Preprint
Publié: 2023
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author Xing, Xin
Lin, Lin
author_facet Xing, Xin
Lin, Lin
contents We provide the first rigorous study of the finite-size error in the simplest and representative coupled cluster theory, namely the coupled cluster doubles (CCD) theory, for gapped periodic systems. Assuming that the CCD equations are solved using exact Hartree-Fock orbitals and orbital energies, we prove that the convergence rate of finite-size error scales as $\mathscr{O}(N_\mathbf{k}^{-\frac13})$, where $N_{\mathbf{k}}$ is the number of discretization point in the Brillouin zone and characterizes the system size. Our analysis shows that the dominant error lies in the coupled cluster amplitude calculation, and the convergence of the finite-size error in energy calculations can be boosted to $\mathscr{O}(N_\mathbf{k}^{-1})$ with accurate amplitudes. This also provides the first proof of the scaling of the finite-size error in the third order Møller-Plesset perturbation theory (MP3) for periodic systems.
format Preprint
id arxiv_https___arxiv_org_abs_2302_06043
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Finite-size effects in periodic coupled cluster calculations
Xing, Xin
Lin, Lin
Numerical Analysis
Chemical Physics
Computational Physics
81Q99, 65G99, 65D32
We provide the first rigorous study of the finite-size error in the simplest and representative coupled cluster theory, namely the coupled cluster doubles (CCD) theory, for gapped periodic systems. Assuming that the CCD equations are solved using exact Hartree-Fock orbitals and orbital energies, we prove that the convergence rate of finite-size error scales as $\mathscr{O}(N_\mathbf{k}^{-\frac13})$, where $N_{\mathbf{k}}$ is the number of discretization point in the Brillouin zone and characterizes the system size. Our analysis shows that the dominant error lies in the coupled cluster amplitude calculation, and the convergence of the finite-size error in energy calculations can be boosted to $\mathscr{O}(N_\mathbf{k}^{-1})$ with accurate amplitudes. This also provides the first proof of the scaling of the finite-size error in the third order Møller-Plesset perturbation theory (MP3) for periodic systems.
title Finite-size effects in periodic coupled cluster calculations
topic Numerical Analysis
Chemical Physics
Computational Physics
81Q99, 65G99, 65D32
url https://arxiv.org/abs/2302.06043