A vibrationally resolved experimental study of the sulfur L-shell photoelectron spectrum of the CS2 molecule
(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.
(Less)
- author
- Wang, H. LU ; Bässler, M. LU ; Hjelte, I. ; Burmeister, F. and Karlsson, L. LU
- organization
- publishing date
- 2001-05-14
- 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
- 2022-03-03 19:07:15
@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}}, }