The low-lying electronic states of 4H-pyran-4-thione; a photoionization and vacuum ultraviolet absorption study, with interpretation by configuration interaction and density functional calculations for the ionic and singlet states.

Michael H. Palmer*, Antti Kivimäki, Søren V. Hoffmann, Nykola C. Jones, Marcello Coreno, Monica de Simone, Cesare Grazioli, R Alan Aitken, Iain L. J. Patterson, Loëlia Perrault

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Two synchrotron-based studies on 4H-pyran-4-thione, photoelectron spectroscopy and vacuum ultraviolet (VUV) absorption spectra were performed. A highly resolved structure was observed in the photoelectron spectrum (PES), in contrast to an earlier PES study, where little structure was observed. The sequence of ionic states was determined using configuration interaction and coupled cluster methods. The vibrational structure of the lowest three PES bands was analyzed by configuration interaction and density functional calculations, providing a detailed explanation of the observed profiles. Several vibrational bands in the VUV absorption spectrum showed a similar structure to the bands in the PES and were identified as Rydberg states.
Original languageEnglish
Article number034304
Number of pages14
JournalJournal of Chemical Physics
Volume162
Issue number3
DOIs
Publication statusPublished - 15 Jan 2025

Keywords

  • Configuration interaction
  • Coupled-cluster methods
  • Density functional theory
  • Excitation energies
  • Rydberg states
  • Vacuum ultraviolet radiation
  • Synchrotrons
  • Absorption spectroscopy
  • Photoelectron spectroscopy
  • Photoionization

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