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231226s2023 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.27093
|2 doi
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|a pubmed24n1177.xml
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|a (NLM)36825673
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|e rakwb
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|a eng
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|a Vörös, Dóra
|e verfasserin
|4 aut
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|a Excited states of ortho-nitrobenzaldehyde as a challenging case for single- and multi-reference electronic structure theory
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|c 2023
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|a Text
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|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|a Date Completed 24.04.2023
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|a Date Revised 24.04.2023
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a © 2023 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.
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|a We present a large set of vertical excitation calculations for the ortho-nitrobenzaldehyde (oNBA) molecule, which exhibits a very challenging excited-state electronic structure like other nitroaromatic compounds. The single-reference methods produce mostly consistent results up to about 5.5 eV. By contrast, the CAS second-order perturbation theory (CASPT2) results depend sensitively on the employed parameters. At the CAS self-consistent field level, the energies of the bright ππ * states are strongly overestimated while doubly excited states appear too low and mix with these ππ * states. This mixing hampers the CASPT2 step, leading to inconsistent results. Only by increasing the number of states in the state-averaging step to about 40-to cover all bright ππ * states embedded in the double excitations-and employing extended multistate CASPT2 could CASPT2 results consistent with experiment be obtained. We assign the four bands in the molecule's spectrum: The weakest band at 3.7 eV arises from the n NO 2 π * states, the second one at 4.4 eV from the ππ * ( L b ) state, the shoulder at 5.2 eV from the ππ * ( L a ) state, and the maximum at 5.7 eV from the ππ * ( B a / B b ) states. We also highlight the importance of modern wave function analysis techniques in elucidating the absorption spectrum of challenging molecules
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|a Journal Article
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|a UV/Vis absorption spectroscopy
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|a excited states
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|a multireference calculations
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|a nitro-aromatic compounds
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|a single-reference calculations
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|a Mai, Sebastian
|e verfasserin
|4 aut
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 44(2023), 14 vom: 30. Mai, Seite 1381-1394
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:44
|g year:2023
|g number:14
|g day:30
|g month:05
|g pages:1381-1394
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|u http://dx.doi.org/10.1002/jcc.27093
|3 Volltext
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