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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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  • Michael H. Palmer, University of Edinburgh, United Kingdom
  • Nykola C. Jones
  • Søren Vrønning Hoffmann
  • R. Alan Aitken, St Andrews University, United Kingdom
  • Marcello Coreno, CNR, Istituto di Struttura della Materia (ISM-CNR), Consiglio Nazionale delle Ricerche (CNR), ISM, LD2 Unit, Italy
  • Monica De Simone, Istituto Officina dei Materiali (IOM-CNR), Italy
  • Cesare Grazioli, Istituto Officina dei Materiali (IOM-CNR), Italy
  • Iain L. J. Patterson, Univ St Andrews, University of St Andrews, Sch Chem, United Kingdom
A new vacuum ultraviolet absorption (VUV) spectrum of azulene vapor has been obtained by using a synchrotron radiation source. The onset of the ultraviolet spectrum, previously reported by Sidman et al., has been analyzed in detail by Franck–Condon (FC) and Herzberg–Teller (HT) methods. The photoelectron spectral profile identifies the 3px-Rydberg state 00 band to be 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 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 profiles are 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. Energies obtained from use of extremely diffuse s-, p-, d-, or f-character functions enabled realistic extrapolation to the IE1 for many Rydberg states (RS). The lowest RS (3b13s) based on IE2 lies at 4.804 eV with a quantum defect of 0.714. Differentiation between valence and RS is readily made using the second moments of the charge distribution.
Original languageEnglish
Article number154307
JournalThe Journal of Chemical Physics
Publication statusPublished - Oct 2022

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