open access publication

Article, 2024

Exploring the low-lying electronic states of C4H6OS isomers, dihydro-2(3H)-thiophenone and dihydro-3(2H)-thiophenone

Journal of Quantitative Spectroscopy and Radiative Transfer, ISSN 1879-1352, 0022-4073, Volume 317, Page 108926, 10.1016/j.jqsrt.2024.108926

Contributors

Kumar, Sarvesh 0000-0002-1996-9925 [1] [2] Duflot, Denis 0000-0002-8307-5344 (Corresponding author) [3] [4] Jones, Nykola C 0000-0002-4081-6405 [5] Hoffmann, Søren Vrønning 0000-0002-8018-5433 [5] Limão-Vieira, Paulo Manuel Assis 0000-0003-2696-1152 (Corresponding author) [2]

Affiliations

  1. [1] Lawrence Berkeley National Laboratory
    2. [NORA names: United States; America, North; OECD];
  2. [2] Universidade Nova de Lisboa
    3. [NORA names: Portugal; Europe, EU; OECD];
  3. [3] French National Centre for Scientific Research
    4. [NORA names: France; Europe, EU; OECD];
  4. [4] University of Lille
    5. [NORA names: France; Europe, EU; OECD];
  5. [5] Aarhus University
    6. [NORA names: AU Aarhus University; University; Denmark; Europe, EU; Nordic; OECD]

Abstract

Results of a detailed study on the electronic state spectroscopy of C4H6OS isomers, dihydro-2(3H)-thiophenone and dihydro-3(2H)-thiophenone, have been obtained from high-resolution vacuum ultraviolet photoabsorption experiments together with quantum chemical calculations. The absolute photoabsorption cross-sections in the 3.7–10.7 eV energy range were obtained at the AU-UV beam line, ASTRID2 synchrotron radiation facility. The absorption spectra exhibit features due to transitions into valence and Rydberg states, superimposed on vibrational fine structure which appear much weaker in the photoabsorption spectrum of dihydro-3(2H)-thiophenone. Assignments have been proposed for some of the absorption bands with the aid of ab initio calculations at the equation-of-motion coupled-cluster singles and doubles level (EOM-CCSD) providing vertical excitation energies and oscillator strengths. The nature of the transitions was assessed by visual inspection of the natural orbitals for each transition and the average values from the electronic radial spatial extents of the electronic cloud. A comparison between the vibrational structure observed in the experimental spectra suggests relevant CO stretching excitations for both molecules, with important CH2 twisting and rocking modes for dihydro-2(3H)-thiophenone and ring stretching modes for dihydro-3(2H)-thiophenone. Photolysis lifetimes from 0 up to 50 km altitude in the Earth's atmosphere for both chemical compounds have been estimated from the absolute photoabsorption cross-sections.

Keywords

CH2, CH2 twisting, EOM-CCSD, Earth, Earth's atmosphere, Radiation Facility, Rydberg, Rydberg states, Synchrotron Radiation Facility, ab initio calculations, absolute photoabsorption cross-sections, absorption, absorption bands, absorption spectra, altitude, assignment, atmosphere, average value, band, beam line, calculations, chemical calculations, chemical compounds, cloud, comparison, compounds, coupled-cluster singles, cross-section, doubling level, electron cloud, electronic state spectroscopy, electronic states, energy, energy range, equation-of-motion coupled-cluster singles, excitation, excitation energy, experimental spectra, experiments, extent, facilities, features, fine structure, initio calculations, inspection, isomers, km altitude, levels, lifetime, lines, mode, molecules, natural orbitals, orbit, oscillations, oscillator strengths, photoabsorption, photoabsorption cross-sections, photoabsorption experiments, photoabsorption spectra, photolysis, photolysis lifetime, quantum chemical calculations, range, results, ring, ring stretching modes, rocking mode, singles, spatial extent, spectra, state, strength, stretch excitation, stretching mode, structure, study, transition, twist, valence, values, vertical excitation energies, vibrational fine structure, vibrational structure, visual inspection

Funders

  • European Cooperation in Science and Technology
  • Fundação para a Ciência e Tecnologia
  • General Electric (United States)
  • Ministry of Higher Education and Research
  • European Commission
  • Agence Nationale de la Recherche

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