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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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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. / Palmer, Michael H.; Jones, Nykola C.; Hoffmann, Søren Vrønning et al.

In: The Journal of Chemical Physics, Vol. 157, No. 15, 154307, 10.2022.

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@article{e82857b51b30411fb14801c580bfe863,
title = "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",
abstract = "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.",
author = "Palmer, {Michael H.} and Jones, {Nykola C.} and Hoffmann, {S{\o}ren Vr{\o}nning} and Aitken, {R. Alan} and Marcello Coreno and {De Simone}, Monica and Cesare Grazioli and Patterson, {Iain L. J.}",
year = "2022",
month = oct,
doi = "10.1063/5.0106697",
language = "English",
volume = "157",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMER INST PHYSICS",
number = "15",

}

RIS

TY - JOUR

T1 - The excited states of azulene

T2 - 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

AU - Palmer, Michael H.

AU - Jones, Nykola C.

AU - Hoffmann, Søren Vrønning

AU - Aitken, R. Alan

AU - Coreno, Marcello

AU - De Simone, Monica

AU - Grazioli, Cesare

AU - Patterson, Iain L. J.

PY - 2022/10

Y1 - 2022/10

N2 - 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.

AB - 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.

U2 - 10.1063/5.0106697

DO - 10.1063/5.0106697

M3 - Journal article

C2 - 36272785

VL - 157

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 15

M1 - 154307

ER -