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

doi:10.1063/5.0243859

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 journal › Article › peer-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 language	English
Article number	034304
Number of pages	14
Journal	Journal of Chemical Physics
Volume	162
Issue number	3
DOIs	https://doi.org/10.1063/5.0243859
Publication status	Published - 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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034304_1_5.0243859
© 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0243859
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Palmer, M. H., Kivimäki, A., Hoffmann, S. V., Jones, N. C., Coreno, M., de Simone, M., Grazioli, C., Aitken, R. A., Patterson, I. L. J., & Perrault, L. (2025). 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. Journal of Chemical Physics, 162(3), Article 034304. https://doi.org/10.1063/5.0243859

@article{7901a5dad0834df387d0120dc18565d1,

title = "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.",

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.",

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

author = "Palmer, \{Michael H.\} and Antti Kivim{\"a}ki and Hoffmann, \{S{\o}ren V.\} and Jones, \{Nykola C.\} and Marcello Coreno and \{de Simone\}, Monica and Cesare Grazioli and Aitken, \{R Alan\} and Patterson, \{Iain L. J.\} and Lo{\"e}lia Perrault",

note = "Funding: Authors acknowledge (a) the ISA, Department of Physics and Astronomy, Aarhus University, for the beam time on the AU-UV beam line in ASTRID2; (b) the MAX IV Laboratory for time on Beamline FinEstBeAMS under in-house proposal Grant No. 20240972; and (c) supercomputing facilities at the University of Edinburgh (Eddie3) and Edinburgh Parallel Computing Center (Cirrus) for support. We thank Kirill Chernenko for assistance in the experiments performed at the FinEstBeAMS beamline. Research conducted at MAX IV, a Swedish national user facility, was supported by the Swedish Research Council under Contract No. 2018-07152, the Swedish Governmental Agency for Innovation Systems under Contract No. 2018-04969, and Formas under Contract No. 2019-02496. Plotting using Origin 7.0;53 MOs were drawn using GaussView;54 AIM densities were evaluated using AIMQB; and the authors thank T. A. Keith for providing this software.51 ",

year = "2025",

month = jan,

day = "15",

doi = "10.1063/5.0243859",

language = "English",

volume = "162",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "3",

}

Palmer, MH, Kivimäki, A, Hoffmann, SV, Jones, NC, Coreno, M, de Simone, M, Grazioli, C, Aitken, RA, Patterson, ILJ & Perrault, L 2025, '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.', Journal of Chemical Physics, vol. 162, no. 3, 034304. https://doi.org/10.1063/5.0243859

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. / Palmer, Michael H.; Kivimäki, Antti; Hoffmann, Søren V. et al.
In: Journal of Chemical Physics, Vol. 162, No. 3, 034304, 15.01.2025.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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.

AU - Palmer, Michael H.

AU - Kivimäki, Antti

AU - Hoffmann, Søren V.

AU - Jones, Nykola C.

AU - Coreno, Marcello

AU - de Simone, Monica

AU - Grazioli, Cesare

AU - Aitken, R Alan

AU - Patterson, Iain L. J.

AU - Perrault, Loëlia

N1 - Funding: Authors acknowledge (a) the ISA, Department of Physics and Astronomy, Aarhus University, for the beam time on the AU-UV beam line in ASTRID2; (b) the MAX IV Laboratory for time on Beamline FinEstBeAMS under in-house proposal Grant No. 20240972; and (c) supercomputing facilities at the University of Edinburgh (Eddie3) and Edinburgh Parallel Computing Center (Cirrus) for support. We thank Kirill Chernenko for assistance in the experiments performed at the FinEstBeAMS beamline. Research conducted at MAX IV, a Swedish national user facility, was supported by the Swedish Research Council under Contract No. 2018-07152, the Swedish Governmental Agency for Innovation Systems under Contract No. 2018-04969, and Formas under Contract No. 2019-02496. Plotting using Origin 7.0;53 MOs were drawn using GaussView;54 AIM densities were evaluated using AIMQB; and the authors thank T. A. Keith for providing this software.51

PY - 2025/1/15

Y1 - 2025/1/15

N2 - 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.

AB - 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.

KW - Configuration interaction

KW - Coupled-cluster methods

KW - Density functional theory

KW - Excitation energies

KW - Rydberg states

KW - Vacuum ultraviolet radiation

KW - Synchrotrons

KW - Absorption spectroscopy

KW - Photoelectron spectroscopy

KW - Photoionization

U2 - 10.1063/5.0243859

DO - 10.1063/5.0243859

M3 - Article

SN - 0021-9606

VL - 162

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 3

M1 - 034304

ER -

Palmer MH, Kivimäki A, Hoffmann SV, Jones NC, Coreno M, de Simone M et al. 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. Journal of Chemical Physics. 2025 Jan 15;162(3):034304. doi: 10.1063/5.0243859