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dc.contributor.authorPalmer, Michael H.
dc.contributor.authorHoffmann, Søren V.
dc.contributor.authorJones, Nykola C.
dc.contributor.authorCoreno, Marcello
dc.contributor.authorde Simone, Monica
dc.contributor.authorGrazioli, Cesare
dc.contributor.authorAitken, R Alan
dc.contributor.authorPeureux, Coralyse
dc.date.accessioned2023-06-28T15:30:10Z
dc.date.available2023-06-28T15:30:10Z
dc.date.issued2023-06-21
dc.identifier.citationPalmer , M H , Hoffmann , S V , Jones , N C , Coreno , M , de Simone , M , Grazioli , C , Aitken , R A & Peureux , C 2023 , ' High-level studies of the singlet and triplet states of quadricyclane, including analysis of a new experimental vacuum ultraviolet absorption spectrum by configuration interaction and density functional calculations ' , Journal of Chemical Physics , vol. 158 , no. 23 , 234303 . https://doi.org/10.1063/5.0151758en
dc.identifier.issn0021-9606
dc.identifier.otherPURE: 286887361
dc.identifier.otherPURE UUID: 8433b336-0588-48e6-865e-afa04f8b2954
dc.identifier.otherORCID: /0000-0001-6959-5311/work/137089055
dc.identifier.otherScopus: 85161984465
dc.identifier.urihttps://hdl.handle.net/10023/27832
dc.description.abstractA synchrotron-based vacuum ultraviolet absorption spectrum (VUV) of quadricyclane (QC) is reported with energies up to 10.8 eV. Extensive vibrational structure has been extracted from the broad maxima by fitting short energy ranges of the VUV spectrum to high level polynomial functions and processing the regular residuals. Comparison of these data with our recent high-resolution photoelectron spectral (PES) of QC showed that this structure must be attributed to Rydberg states. Several of these appear before the valence states at higher energies. Both types of states have been calculated by configuration interaction (CI), including symmetry-adapted cluster studies (SAC-CI), and time dependent density functional theoretical methods (TDDFT). There is a close correlation between the SAC-CI vertical excitation energies (VEE) and both B3LYP and especially CAM-B3LYP determined ones. The VEE for several low-lying s-, p-, d- and f-Rydberg states (RS), have been determined by SAC-CI and adiabatic excitation energies (AEE) by TDDFT methods. Searches for equilibrium structures for 11,3A2, and 11B1 states for QC led to rearrangement to a norbornadiene structure. Determination of the experimental 00 band positions, which show very low cross-sections, has been assisted by matching features in the spectra with Franck-Condon fits. Herzberg-Teller vibrational profiles for the Rydberg states are relatively more intense than the FC ones, but only at high energy, and are attributed to up to 10 quanta. The vibrational fine structure of the RS calculated by both FC and HT procedures, gives an easy route into generating HT profiles for ionic states, which usually require non-standard procedures.
dc.format.extent12
dc.language.isoeng
dc.relation.ispartofJournal of Chemical Physicsen
dc.rightsCopyright © 2023 the Authors. This work has been made available online in accordance with the Rights Retention Strategy. This accepted manuscript is distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. The final published version of this work is available at https://doi.org/10.1063/5.0151758en
dc.subjectQD Chemistryen
dc.subjectQC Physicsen
dc.subjectNDASen
dc.subjectMCCen
dc.subject.lccQDen
dc.subject.lccQCen
dc.titleHigh-level studies of the singlet and triplet states of quadricyclane, including analysis of a new experimental vacuum ultraviolet absorption spectrum by configuration interaction and density functional calculationsen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1063/5.0151758
dc.description.statusPeer revieweden


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