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

M Michael H. Palmer (School of Chemistry, University of Edinburgh 1 , Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland,) A Antti Kivimäki (MAX IV Laboratory, Lund University 2 , SE-22100 Lund,) S Søren Vrønning Hoffmann (ISA, Department of Physics and Astronomy, Aarhus University 2 , Ny Munkegade 120, DK-8000 Aarhus C,) N Nykola C. Jones (ISA, Department of Physics and Astronomy, Aarhus University 2 , Ny Munkegade 120, DK-8000 Aarhus C,) M Marcello Coreno (CNR–Istituto di Struttura della Materia (ISM), Basovizza, Trieste 34149, Italy) M Monica de Simone (IOM-CNR, Istituto Officina dei Materiali 4 , Basovizza SS-14, Km 163.5, 34149 Trieste,) C Cesare Grazioli (CNR–Istituto Officina dei Materiali (IOM), Basovizza, Trieste 34149, Italy) R R. Alan Aitken (School of Chemistry, University of St Andrews 5 , North Haugh, St Andrews, Fife KY16 9ST, Scotland,) I Iain L. J. Patterson (School of Chemistry, University of St Andrews 5 , North Haugh, St Andrews, Fife KY16 9ST, Scotland,) L Loëlia Perrault (School of Chemistry, University of St Andrews 6 , North Haugh, Fife, St Andrews KY16 9ST,)

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.

Article Details

Volume / Issue Vol. 162, Issue 3
Published January 21, 2025
ISSN 0021-9606
Publisher American Institute of Physics

Journal Info

The Journal of Chemical Physics

American Institute of Physics

ISSN: 0021-9606 Physical Sciences

Authors (10)

M

Michael H. Palmer

School of Chemistry, University of Edinburgh 1 , Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland,

A

Antti Kivimäki

MAX IV Laboratory, Lund University 2 , SE-22100 Lund,

S

Søren Vrønning Hoffmann

ISA, Department of Physics and Astronomy, Aarhus University 2 , Ny Munkegade 120, DK-8000 Aarhus C,

N

Nykola C. Jones

ISA, Department of Physics and Astronomy, Aarhus University 2 , Ny Munkegade 120, DK-8000 Aarhus C,

M

Marcello Coreno

CNR–Istituto di Struttura della Materia (ISM), Basovizza, Trieste 34149, Italy

M

Monica de Simone

IOM-CNR, Istituto Officina dei Materiali 4 , Basovizza SS-14, Km 163.5, 34149 Trieste,

C

Cesare Grazioli

CNR–Istituto Officina dei Materiali (IOM), Basovizza, Trieste 34149, Italy

R

R. Alan Aitken

School of Chemistry, University of St Andrews 5 , North Haugh, St Andrews, Fife KY16 9ST, Scotland,

I

Iain L. J. Patterson

School of Chemistry, University of St Andrews 5 , North Haugh, St Andrews, Fife KY16 9ST, Scotland,

L

Loëlia Perrault

School of Chemistry, University of St Andrews 6 , North Haugh, Fife, St Andrews KY16 9ST,