The performance of several methods for the calculation of vertical ionization potentials (IPs) or, more generally, electron-detachment energies based on unitary coupled-cluster (UCC) theory and the algebraic-diagrammatic construction (ADC) scheme is evaluated with respect to benchmark data computed at the level of equation-of-motion coupled-cluster theory, including single, double, and triple excitations (IP-EOM-CCSDT). Based on a statistical evaluation of about 200 electron-detached states of 41 molecules, the second-order methods IP-ADC(2) and IP-UCC2 show modest accuracies with IP-EOM-CCSDT as reference, exposing a mean signed error and a standard deviation of the error of −0.54 ± 0.50 and −0.49 ± 0.54 eV, respectively, accompanied by a mean absolute error (MAE) of 0.61 and 0.58 eV, respectively. The strict third-order IP-ADC method demonstrates an accuracy of 0.26 ± 0.35 eV (MAE = 0.35 eV), while the IP-UCC3 method is slightly more accurate with 0.24 ± 0.26 eV (MAE = 0.29 eV). Employing the static self-energy computed using the Dyson expansion method (DEM) improves the IP-ADC(3) performance to 0.27 ± 0.28 eV, with the mean absolute error of this method being 0.32 eV. However, employing the simpler improved fourth-order scheme Σ(4+) for the static self-energy provides almost identical results as the DEM. Based on the quality of the present benchmark results, it therefore appears not necessary to use the computationally more demanding DEM.
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7 February 2022
Research Article|
February 04 2022
Vertical ionization potential benchmark for unitary coupled-cluster and algebraic-diagrammatic construction methods
Adrian L. Dempwolff
;
Adrian L. Dempwolff
a)
1
Interdisciplinary Center for Scientific Computing, Heidelberg University
, Im Neuenheimer Feld 205, 69120 Heidelberg, Germany
a)Author to whom correspondence should be addressed: [email protected]
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Manuel Hodecker
;
Manuel Hodecker
1
Interdisciplinary Center for Scientific Computing, Heidelberg University
, Im Neuenheimer Feld 205, 69120 Heidelberg, Germany
2
Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology
, Malvinas Väg 10, 114 28 Stockholm, Sweden
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Andreas Dreuw
Andreas Dreuw
1
Interdisciplinary Center for Scientific Computing, Heidelberg University
, Im Neuenheimer Feld 205, 69120 Heidelberg, Germany
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 156, 054114 (2022)
Article history
Received:
November 17 2021
Accepted:
January 16 2022
Citation
Adrian L. Dempwolff, Manuel Hodecker, Andreas Dreuw; Vertical ionization potential benchmark for unitary coupled-cluster and algebraic-diagrammatic construction methods. J. Chem. Phys. 7 February 2022; 156 (5): 054114. https://doi.org/10.1063/5.0079047
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