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The excited states of azulene : a study of the vibrational energy levels for the lower ππ*-valence states by configuration interaction and density functional calculations, and theoretical studies of the Rydberg states

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Date
20/10/2022
Author
Palmer, Michael H
Jones, Nykola C
Hoffmann, Soren V
Aitken, R Alan
Coreno, Marcello
de Simone, Monica
Grazioli, Cesare
Patterson, Iain
Keywords
QC Physics
QD Chemistry
NDAS
MCC
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Abstract
A new vacuum ultraviolet absorption spectrum of azulene vapour has been obtained by using a synchrotron radiation source.The onset of the ultraviolet spectrum, previously reported by Sidman et al has been analysed in detail by Franck-Condon (FC) and Herzberg-Teller (HT) methods. The PES profile identifies the 3px-Rydberg state 00 band as 131 cm-1 from the VUV maximum. Excited state energy levels were calculated by three independent methods: the wide scan VUV spectrum was correlated with symmetry adapted cluster configuration interaction (SAC-CI) calculations. The low energy portion of the spectrum was studied by both time dependent density functional theoretical methods (TDDFT) and multi-reference multi-root CI (MRD-CI). Equilibrium structures were determined for valence states at the TDDFT level. Rydberg states were determined by both TDDFT and MRD-CI. The FC+HT analyses were performed on the TDDFT wave-functions. The HT intensity profile is generally low in intensity, relative to the FC ones; however, HT is dominant in the second singlet state (S2, 11A1). As a result, numerous non-symmetric modes, their overtones and combination bands show considerable intensity in that band. Extremely diffuse s-, p-, d- or f-character functions enabled extrapolation to the IE1 for many Rydberg states (RS). The lowest RS based on IE2 (3b13s) lies at 4.804 eV with quantum defect 0.714. Differentiation between valence and RS is readily made using the second moments of the charge distribution.
Citation
Palmer , M H , Jones , N C , Hoffmann , S V , Aitken , R A , Coreno , M , de Simone , M , Grazioli , C & Patterson , I 2022 , ' The excited states of azulene : a study of the vibrational energy levels for the lower ππ*-valence states by configuration interaction and density functional calculations, and theoretical studies of the Rydberg states ' , The Journal of Chemical Physics , vol. 157 , no. 15 , 154307 . https://doi.org/10.1063/5.0106697
Publication
The Journal of Chemical Physics
Status
Peer reviewed
DOI
https://doi.org/10.1063/5.0106697
ISSN
0021-9606
Type
Journal article
Rights
Copyright © 2022 The Author(s). Published under an exclusive license by AIP Publishing. 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/10.1063/5.0106697
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/26341

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