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Vertical ionization...
Vertical ionization potential benchmark for unitary coupled-cluster and algebraic-diagrammatic construction methods
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- Dempwolff, Adrian L. (author)
- Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany.
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- Hodecker, Manuel (author)
- KTH,Teoretisk kemi och biologi,Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany.
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- Dreuw, Andreas (author)
- Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany.
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Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany Teoretisk kemi och biologi (creator_code:org_t)
- AIP Publishing, 2022
- 2022
- English.
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 156:5, s. 054114-
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Abstract
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- 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 & PLUSMN; 0.50 and -0.49 & PLUSMN; 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 & PLUSMN; 0.35 eV (MAE = 0.35 eV), while the IP-UCC3 method is slightly more accurate with 0.24 & PLUSMN; 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 & PLUSMN; 0.28 eV, with the mean absolute error of this method being 0.32 eV. However, employing the simpler improved fourth-order scheme sigma(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.
Subject headings
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
Publication and Content Type
- ref (subject category)
- art (subject category)
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