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Poul Jørgensen

Convergence patterns and rates in two-state perturbation expansions

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Convergence patterns and rates in two-state perturbation expansions. / Olsen, Jeppe; Jørgensen, Poul.

I: Journal of Chemical Physics, Bind 151, Nr. 8, 084108, 08.2019.

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avisTidsskriftartikelForskningpeer review

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@article{f315172c3e524bd8b2e80e4893205786,
title = "Convergence patterns and rates in two-state perturbation expansions",
abstract = "A simple two-state model has previously been shown to be able to describe and rationalize the convergence of the most common perturbation method for including electron correlation, the M{\o}ller-Plesset expansion. In particular, this simple model has been able to predict the convergence rate and the form of the higher-order corrections for typical M{\o}ller-Plesset expansions of the correlation energy. In this paper, the convergence of nondegenerate perturbation expansions in the two-state model is analyzed in detail for a general form of two-state perturbation expansion by examining the analytic expressions of the corrections and series of the values of the corrections for various choices of the perturbation. The previous analysis that covered only a single form of the perturbation is thereby generalized to arbitrary forms of the perturbation. It is shown that the convergence may be described in terms of four characteristics: archetype, rate of convergence, length of recurring period, and sign pattern. The archetype defines the overall form of a plot of the energy-corrections, and the remaining characteristics specify details of the archetype. For symmetric (Hermitian) perturbations, five archetypes are observed: zigzag, interspersed zigzag, triadic, ripples, and geometric. Two additional archetypes are obtained for an asymmetric perturbation: zigzag-geometric and convex-geometric. For symmetric perturbations, each archetype has a distinctive pattern that recurs with a period which depends on the perturbation parameters, whereas no such recurrence exists for asymmetric perturbations from a series of numerical corrections. The obtained relations between the form of a two-state perturbation and the energy corrections allow us to obtain additional insights into the convergence behavior of the M{\o}ller-Plesset and other forms of perturbation expansions. This is demonstrated by analyzing several diverging or slowly converging perturbation expansions of ground state and excitation energies. It is demonstrated that the higher-order corrections of these expansions can be described using the two-state model and each expansion can therefore be described in terms of an archetype and the other three characteristics. Examples of all archetypes except the zigzag and convex-geometric archetypes are given. For each example, it is shown how the characteristics may be extracted from the higher-order corrections and used to identify the term in the perturbation that is the cause of the observed slow convergence or divergence.",
author = "Jeppe Olsen and Poul J{\o}rgensen",
year = "2019",
month = aug,
doi = "10.1063/1.5110554",
language = "English",
volume = "151",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMER INST PHYSICS",
number = "8",

}

RIS

TY - JOUR

T1 - Convergence patterns and rates in two-state perturbation expansions

AU - Olsen, Jeppe

AU - Jørgensen, Poul

PY - 2019/8

Y1 - 2019/8

N2 - A simple two-state model has previously been shown to be able to describe and rationalize the convergence of the most common perturbation method for including electron correlation, the Møller-Plesset expansion. In particular, this simple model has been able to predict the convergence rate and the form of the higher-order corrections for typical Møller-Plesset expansions of the correlation energy. In this paper, the convergence of nondegenerate perturbation expansions in the two-state model is analyzed in detail for a general form of two-state perturbation expansion by examining the analytic expressions of the corrections and series of the values of the corrections for various choices of the perturbation. The previous analysis that covered only a single form of the perturbation is thereby generalized to arbitrary forms of the perturbation. It is shown that the convergence may be described in terms of four characteristics: archetype, rate of convergence, length of recurring period, and sign pattern. The archetype defines the overall form of a plot of the energy-corrections, and the remaining characteristics specify details of the archetype. For symmetric (Hermitian) perturbations, five archetypes are observed: zigzag, interspersed zigzag, triadic, ripples, and geometric. Two additional archetypes are obtained for an asymmetric perturbation: zigzag-geometric and convex-geometric. For symmetric perturbations, each archetype has a distinctive pattern that recurs with a period which depends on the perturbation parameters, whereas no such recurrence exists for asymmetric perturbations from a series of numerical corrections. The obtained relations between the form of a two-state perturbation and the energy corrections allow us to obtain additional insights into the convergence behavior of the Møller-Plesset and other forms of perturbation expansions. This is demonstrated by analyzing several diverging or slowly converging perturbation expansions of ground state and excitation energies. It is demonstrated that the higher-order corrections of these expansions can be described using the two-state model and each expansion can therefore be described in terms of an archetype and the other three characteristics. Examples of all archetypes except the zigzag and convex-geometric archetypes are given. For each example, it is shown how the characteristics may be extracted from the higher-order corrections and used to identify the term in the perturbation that is the cause of the observed slow convergence or divergence.

AB - A simple two-state model has previously been shown to be able to describe and rationalize the convergence of the most common perturbation method for including electron correlation, the Møller-Plesset expansion. In particular, this simple model has been able to predict the convergence rate and the form of the higher-order corrections for typical Møller-Plesset expansions of the correlation energy. In this paper, the convergence of nondegenerate perturbation expansions in the two-state model is analyzed in detail for a general form of two-state perturbation expansion by examining the analytic expressions of the corrections and series of the values of the corrections for various choices of the perturbation. The previous analysis that covered only a single form of the perturbation is thereby generalized to arbitrary forms of the perturbation. It is shown that the convergence may be described in terms of four characteristics: archetype, rate of convergence, length of recurring period, and sign pattern. The archetype defines the overall form of a plot of the energy-corrections, and the remaining characteristics specify details of the archetype. For symmetric (Hermitian) perturbations, five archetypes are observed: zigzag, interspersed zigzag, triadic, ripples, and geometric. Two additional archetypes are obtained for an asymmetric perturbation: zigzag-geometric and convex-geometric. For symmetric perturbations, each archetype has a distinctive pattern that recurs with a period which depends on the perturbation parameters, whereas no such recurrence exists for asymmetric perturbations from a series of numerical corrections. The obtained relations between the form of a two-state perturbation and the energy corrections allow us to obtain additional insights into the convergence behavior of the Møller-Plesset and other forms of perturbation expansions. This is demonstrated by analyzing several diverging or slowly converging perturbation expansions of ground state and excitation energies. It is demonstrated that the higher-order corrections of these expansions can be described using the two-state model and each expansion can therefore be described in terms of an archetype and the other three characteristics. Examples of all archetypes except the zigzag and convex-geometric archetypes are given. For each example, it is shown how the characteristics may be extracted from the higher-order corrections and used to identify the term in the perturbation that is the cause of the observed slow convergence or divergence.

UR - http://www.scopus.com/inward/record.url?scp=85071780623&partnerID=8YFLogxK

U2 - 10.1063/1.5110554

DO - 10.1063/1.5110554

M3 - Journal article

C2 - 31470707

AN - SCOPUS:85071780623

VL - 151

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

M1 - 084108

ER -