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Benchmarking CASPT3 Vertical Excitation Energies

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Title: Benchmarking CASPT3 Vertical Excitation Energies
Authors: Boggio-Pasqua, Martial, Jacquemin, Denis, Loos, Pierre-François
Source: J. Chem. Phys. 157, 014103 (2022)
Publication Year: 2022
Collection: Condensed Matter
Nuclear Theory
Physics (Other)
Subject Terms: Physics - Chemical Physics, Condensed Matter - Strongly Correlated Electrons, Nuclear Theory
More Details: Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to\pi^*$, $\pi\to\pi^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of $0.11$ eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction of the mean absolute error to $0.09$ eV when the IPEA shift is switched off.
Comment: 12 pages, 3 figures (supplementary material available)
Document Type: Working Paper
DOI: 10.1063/5.0095887
Access URL: http://arxiv.org/abs/2204.06480
Accession Number: edsarx.2204.06480
Database: arXiv
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  Data: Benchmarking CASPT3 Vertical Excitation Energies
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  Data: <searchLink fieldCode="AR" term="%22Boggio-Pasqua%2C+Martial%22">Boggio-Pasqua, Martial</searchLink><br /><searchLink fieldCode="AR" term="%22Jacquemin%2C+Denis%22">Jacquemin, Denis</searchLink><br /><searchLink fieldCode="AR" term="%22Loos%2C+Pierre-François%22">Loos, Pierre-François</searchLink>
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  Data: J. Chem. Phys. 157, 014103 (2022)
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  Data: Condensed Matter<br />Nuclear Theory<br />Physics (Other)
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  Data: Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to\pi^*$, $\pi\to\pi^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of $0.11$ eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction of the mean absolute error to $0.09$ eV when the IPEA shift is switched off.<br />Comment: 12 pages, 3 figures (supplementary material available)
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      – TitleFull: Benchmarking CASPT3 Vertical Excitation Energies
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