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A vibrationally resolved experimental study of the sulfur L-shell photoelectron spectrum of the CS2 molecule

Wang, H. LU ; Bässler, M. LU ; Hjelte, I. ; Burmeister, F. and Karlsson, L. LU (2001) In Journal of Physics B: Atomic, Molecular and Optical Physics 34(9). p.1745-1755
Abstract

The sulfur L-shell photoelectron spectrum of the carbon disulfide molecule has been studied using monochromated synchrotron radiation with a photon energy of 250 eV. The spectrum is atomic like, showing three major bands that can be associated with the sulfur (2p-1)2P3/2,12 and (2s-1)2S1/2 ionic states. A closer inspection shows that the 2P3/2 state is further split into two components separated by 128 meV due to the molecular field. The resulting ionic states are located at 169.806 eV (0-0 energy), 169.934 eV (0-0 energy), 171.075 eV (0-0 energy) and 237.05 ± 0.2 eV (centroid), respectively. Vibrational progressions in the (2p-1) bands... (More)

The sulfur L-shell photoelectron spectrum of the carbon disulfide molecule has been studied using monochromated synchrotron radiation with a photon energy of 250 eV. The spectrum is atomic like, showing three major bands that can be associated with the sulfur (2p-1)2P3/2,12 and (2s-1)2S1/2 ionic states. A closer inspection shows that the 2P3/2 state is further split into two components separated by 128 meV due to the molecular field. The resulting ionic states are located at 169.806 eV (0-0 energy), 169.934 eV (0-0 energy), 171.075 eV (0-0 energy) and 237.05 ± 0.2 eV (centroid), respectively. Vibrational progressions in the (2p-1) bands are attributed to the asymmetric v3 mode, which gives evidence of a localization of the core hole. The following values were obtained for the vibrational constants: ωe = 196.7 ± 1.1 meV; ωdxe = 0.2 ± 0.5 meV. A curve fit of the vibrational lines using a Voigt function gave a natural width of 59.6 ± 1.8 meV for the (2p-1) states, corresponding to a lifetime of 11 fs, and a spectrometer broadening of 38.2 ± 1.8 meV. The (2p-1) bands are accompanied by shake-up structures occurring at 6-18 eV higher energies. They are interpreted mainly in terms of excitations to the unoccupied 3πu* orbital in the final ionic state. The (2s-1)2S1/2 band is broad and structureless due to fast Coster-Kronig processes. A fitting of a Voigt function gives a natural line-width of 1.85 eV which corresponds to a lifetime of 0.4 fs.

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organization
publishing date
type
Contribution to journal
publication status
published
in
Journal of Physics B: Atomic, Molecular and Optical Physics
volume
34
issue
9
pages
11 pages
publisher
IOP Publishing
external identifiers
  • scopus:0035858311
ISSN
0953-4075
DOI
10.1088/0953-4075/34/9/311
language
English
LU publication?
yes
id
e6256a5a-ffcc-44da-a2b1-866bfafeee6c
date added to LUP
2020-10-29 18:09:12
date last changed
2021-02-17 05:10:59
@article{e6256a5a-ffcc-44da-a2b1-866bfafeee6c,
  abstract     = {<p>The sulfur L-shell photoelectron spectrum of the carbon disulfide molecule has been studied using monochromated synchrotron radiation with a photon energy of 250 eV. The spectrum is atomic like, showing three major bands that can be associated with the sulfur (2p<sup>-1</sup>)<sup>2</sup>P<sub>3/2,12</sub> and (2s<sup>-1</sup>)<sup>2</sup>S<sub>1/2</sub> ionic states. A closer inspection shows that the <sup>2</sup>P<sub>3/2</sub> state is further split into two components separated by 128 meV due to the molecular field. The resulting ionic states are located at 169.806 eV (0-0 energy), 169.934 eV (0-0 energy), 171.075 eV (0-0 energy) and 237.05 ± 0.2 eV (centroid), respectively. Vibrational progressions in the (2p<sup>-1</sup>) bands are attributed to the asymmetric v<sub>3</sub> mode, which gives evidence of a localization of the core hole. The following values were obtained for the vibrational constants: ω<sub>e</sub> = 196.7 ± 1.1 meV; ω<sub>d</sub>x<sub>e</sub> = 0.2 ± 0.5 meV. A curve fit of the vibrational lines using a Voigt function gave a natural width of 59.6 ± 1.8 meV for the (2p<sup>-1</sup>) states, corresponding to a lifetime of 11 fs, and a spectrometer broadening of 38.2 ± 1.8 meV. The (2p<sup>-1</sup>) bands are accompanied by shake-up structures occurring at 6-18 eV higher energies. They are interpreted mainly in terms of excitations to the unoccupied 3π<sub>u</sub>* orbital in the final ionic state. The (2s<sup>-1</sup>)<sup>2</sup>S<sub>1/2</sub> band is broad and structureless due to fast Coster-Kronig processes. A fitting of a Voigt function gives a natural line-width of 1.85 eV which corresponds to a lifetime of 0.4 fs.</p>},
  author       = {Wang, H. and Bässler, M. and Hjelte, I. and Burmeister, F. and Karlsson, L.},
  issn         = {0953-4075},
  language     = {eng},
  month        = {05},
  number       = {9},
  pages        = {1745--1755},
  publisher    = {IOP Publishing},
  series       = {Journal of Physics B: Atomic, Molecular and Optical Physics},
  title        = {A vibrationally resolved experimental study of the sulfur L-shell photoelectron spectrum of the CS<sub>2</sub> molecule},
  url          = {http://dx.doi.org/10.1088/0953-4075/34/9/311},
  doi          = {10.1088/0953-4075/34/9/311},
  volume       = {34},
  year         = {2001},
}