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

Research output: Contribution to journalJournal articleResearchpeer-review

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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 languageEnglish
JournalJournal of Computational Chemistry
Volume41
Issue number1
Pages (from-to)43-55
Number of pages13
ISSN0192-8651
DOIs
Publication statusPublished - 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

Cite this

@article{741f80275ebf4b2a8de9cb87364e618d,
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",
keywords = "RPA(D), HRPA(D), Singlet, Triplet, Excited states",
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. {\circledC} 2019 The Authors.Journal of Computational Chemistrypublished by WileyPeriodicals, Inc.",
year = "2020",
doi = "10.1002/jcc.26074",
language = "English",
volume = "41",
pages = "43--55",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "JohnWiley & Sons, Inc.",
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}

Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies. / Haase, Pi A. B.; Faber, Rasmus; Provasi, Patricio F.; Sauer, Stephan P. A.

In: Journal of Computational Chemistry, Vol. 41, No. 1, 2020, p. 43-55.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies

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

U2 - 10.1002/jcc.26074

DO - 10.1002/jcc.26074

M3 - Journal article

VL - 41

SP - 43

EP - 55

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

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ER -