Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies

Pablo Baudin; Filip Pawłowski; Dmytro Bykov; Dmitry Liakh; Kasper Kristensen; Jeppe Olsen; Poul Jørgensen

doi:10.1063/1.5046935

Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies

Pablo Baudin, Filip Pawłowski, Dmytro Bykov, Dmitry Liakh, Kasper Kristensen, Jeppe Olsen, Poul Jørgensen

Department of Chemistry

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

22 Citations (Scopus)

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Abstract

The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.

Original language	English
Article number	134110
Journal	Journal of Chemical Physics
Volume	150
Issue	13
Number of pages	23
ISSN	0021-9606
DOIs	https://doi.org/10.1063/1.5046935
Publication status	Published - 2019

Keywords

3RD-ORDER
BASIS-SETS
CONFIGURATION-INTERACTION SINGLES
ELECTRONIC-STRUCTURE
EXCITED-STATES
MODEL
POLARIZATION PROPAGATOR
RESPONSE FUNCTIONS
TRANSITION-PROBABILITIES
WAVE-FUNCTION

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Cluster perturbation theory. III. Perturbation series for coupled cluster singles and doubles excitation energiesFinal published version, 1.55 MBLicence: Other

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title = "Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies",

abstract = "The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.",

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author = "Pablo Baudin and Filip Paw{\l}owski and Dmytro Bykov and Dmitry Liakh and Kasper Kristensen and Jeppe Olsen and Poul J{\o}rgensen",

year = "2019",

doi = "10.1063/1.5046935",

language = "English",

volume = "150",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

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Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies. / Baudin, Pablo; Pawłowski, Filip; Bykov, Dmytro et al.
In: Journal of Chemical Physics, Vol. 150, No. 13, 134110, 2019.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Cluster perturbation theory

T2 - III. Perturbation series for coupled cluster singles and doubles excitation energies

AU - Baudin, Pablo

AU - Pawłowski, Filip

AU - Bykov, Dmytro

AU - Liakh, Dmitry

AU - Kristensen, Kasper

AU - Olsen, Jeppe

AU - Jørgensen, Poul

PY - 2019

Y1 - 2019

N2 - The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.

AB - The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.

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KW - BASIS-SETS

KW - CONFIGURATION-INTERACTION SINGLES

KW - ELECTRONIC-STRUCTURE

KW - EXCITED-STATES

KW - MODEL

KW - POLARIZATION PROPAGATOR

KW - RESPONSE FUNCTIONS

KW - TRANSITION-PROBABILITIES

KW - WAVE-FUNCTION

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DO - 10.1063/1.5046935

M3 - Journal article

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AN - SCOPUS:85063882777

SN - 0021-9606

VL - 150

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 13

M1 - 134110

ER -

Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies

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