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dc.contributor.authorPalmer, Michael H
dc.contributor.authorCoreno, Marcello
dc.contributor.authorde Simone, Monica
dc.contributor.authorGrazioli, Cesare
dc.contributor.authorAitken, R Alan
dc.contributor.authorHoffmann, Søren V
dc.contributor.authorJones, Nykola C
dc.contributor.authorPeureux, Coralyse
dc.date.accessioned2020-12-07T15:58:14Z
dc.date.available2020-12-07T15:58:14Z
dc.date.issued2020-11-30
dc.identifier.citationPalmer , M H , Coreno , M , de Simone , M , Grazioli , C , Aitken , R A , Hoffmann , S V , Jones , N C & Peureux , C 2020 , ' High-level studies of the ionic states of norbornadiene and quadricyclane, including analysis of new experimental photoelectron spectra by configuration interaction and coupled cluster calculations ' , The Journal of Chemical Physics , vol. 153 , no. 20 , 204303 . https://doi.org/10.1063/5.0031387en
dc.identifier.issn0021-9606
dc.identifier.otherPURE: 271085498
dc.identifier.otherPURE UUID: 66675588-2ab6-41d7-939b-5e663eff35e9
dc.identifier.otherORCID: /0000-0001-6959-5311/work/84753132
dc.identifier.otherScopus: 85097036973
dc.identifier.otherWOS: 000596592200002
dc.identifier.urihttp://hdl.handle.net/10023/21094
dc.description.abstractSynchrotron-based photoelectron spectra (PES) of norbornadiene (NBD) and quadricyclane (QC) differ significantly from those in previous studies. The adiabatic ionization energy (AIE1) for NBD, assigned to the 2B1 state at 8.279 eV, shows a progression of 18 members with decreasing vibration frequency from 390 cm−1 to 340 cm−1; our calculated frequency is 381 cm−1. Similarly, the AIE1 for QC at 7.671 eV, assigned to the 2B2 state, discloses a vibrational progression of nine or more members with vibration frequency decreasing from 703 cm−1 to 660 cm−1; our calculated vibration frequency is 663 cm−1. These AIEs, determined by coupled cluster and fourth order Møller–Plesset perturbation theory, were very similar to the corresponding second order perturbation theory results. The calculated AIE symmetry sequences are 2B1 < 2A1 < 2A2 < 2B2 for NBD and 2B2 < 2A2 < 2B1 < 2A1 for QC. The overall PES vertical ionization energy profiles for both compounds were closely reproduced by Tamm–Dancoff approximation energies and intensities. The vibrational structure of the ionic states, determined using Franck–Condon methods, gave a good account of the observed spectra, but the observed envelopes for both IE1 are complex sets of vibrations, rather than single progressions. The NMR spectra for QC showed residual second order properties at 300 MHz; both QC and NBD have been theoretically analyzed in greater detail using AA/BB/CC/XX/ spectra, where all H are coupled; the magnetic shielding and spin–spin coupling constants obtained are similar to experimental values.
dc.format.extent16
dc.language.isoeng
dc.relation.ispartofThe Journal of Chemical Physicsen
dc.rightsCopyright © 2020 The Author(s). This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1063/5.0031387en
dc.subjectQD Chemistryen
dc.subjectNDASen
dc.subject.lccQDen
dc.titleHigh-level studies of the ionic states of norbornadiene and quadricyclane, including analysis of new experimental photoelectron spectra by configuration interaction and coupled cluster calculationsen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1063/5.0031387
dc.description.statusPeer revieweden


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