Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies

Pi A. B. Haase; Rasmus Faber; Patricio F. Provasi; Stephan P. A. Sauer

doi:10.1002/jcc.26074

Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies

Pi A. B. Haase^*, Rasmus Faber, Patricio F. Provasi, Stephan P. A. Sauer

^*Corresponding author for this work

Department of Chemistry

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Abstract

The second‐order noniterative doubles‐corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles‐corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second‐order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second‐order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time

Original language	English
Journal	Journal of Computational Chemistry
Volume	41
Issue number	1
Pages (from-to)	43-55
Number of pages	13
ISSN	0192-8651
DOIs	https://doi.org/10.1002/jcc.26074
Publication status	Published - 2020

Bibliographical note

This is an open access article under the terms of the Creative CommonsAttribution License, which permits use, distribution and reproduction in anymedium, provided the original work is properly cited. © 2019 The Authors.Journal of Computational Chemistrypublished by WileyPeriodicals, Inc.

Keywords

RPA(D)
HRPA(D)
Singlet
Triplet
Excited states

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title = "Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies",

abstract = "The second‐order noniterative doubles‐corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles‐corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second‐order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second‐order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time",

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author = "Haase, {Pi A. B.} and Rasmus Faber and Provasi, {Patricio F.} and Sauer, {Stephan P. A.}",

note = "This is an open access article under the terms of the Creative CommonsAttribution License, which permits use, distribution and reproduction in anymedium, provided the original work is properly cited. {\textcopyright} 2019 The Authors.Journal of Computational Chemistrypublished by WileyPeriodicals, Inc.",

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AU - Haase, Pi A. B.

AU - Faber, Rasmus

AU - Provasi, Patricio F.

AU - Sauer, Stephan P. A.

N1 - This is an open access article under the terms of the Creative CommonsAttribution License, which permits use, distribution and reproduction in anymedium, provided the original work is properly cited. © 2019 The Authors.Journal of Computational Chemistrypublished by WileyPeriodicals, Inc.

PY - 2020

Y1 - 2020

N2 - The second‐order noniterative doubles‐corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles‐corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second‐order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second‐order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time

AB - The second‐order noniterative doubles‐corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles‐corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second‐order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second‐order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time

KW - RPA(D)

KW - HRPA(D)

KW - Singlet

KW - Triplet

KW - Excited states

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M3 - Journal article

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SN - 0192-8651

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EP - 55

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 1

ER -

Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies

Abstract

Bibliographical note

Keywords

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