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

Kumar, S.; Duflot, D.; Jones, N. C.; Hoffmann, S. V.; Limão-Vieira, P.

http://hdl.handle.net/10362/172616

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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 C[dbnd]O 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.

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PLV also acknowledges his visiting professor position at Federal University of Paraná, Curitiba, Brazil. The authors wish to acknowledge the beam time at the ISA synchrotron, Aarhus University, Denmark. This contribution is also based upon work from the COST Action CA18212-Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology). DD acknowledges support from the CaPPA project (Chemical and Physical Properties of the Atmosphere) funded by the French National Research Agency (ANR) through the PIA (Programme d'Investissement d'Avenir) under contract no. ANR-10-LABX-005 ; the Région Hauts de France and the Ministère de l'Enseignement Supérieur et de la Recherche (CPER ECRIN) and the European Fund for Regional Economic Development for their financial support. This work was performed using HPC resources from GENCI-TGCC (Grant No. 2023–A0130801859 ) and the Centre de Ressources Informatiques (CRI) of the Université de Lille. Publisher Copyright: © 2024 The Author(s)

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Cross section Dihydro-2(3H)-thiophenone Dihydro-3(2H)-thiophenone Photoabsorption Rydberg states VUV Radiation Atomic and Molecular Physics, and Optics Spectroscopy