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The electronic structure of free water clusters probed by Auger electron spectroscopy

Ohrwall, G; Fink, RF; Tchaplyguine, Maxim LU ; Ojamae, L; Lundwall, M; Marinho, RRT; de Brito, AN; Ristinmaa Sörensen, Stacey LU ; Gisselbrecht, Mathieu LU and Feifel, R, et al. (2005) In Journal of Chemical Physics 123(5).
Abstract
(H2O)(N) clusters generated in a supersonic expansion source with N similar to 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these... (More)
(H2O)(N) clusters generated in a supersonic expansion source with N similar to 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states-the water dimer and a 20-molecule water cluster-were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES. (Less)
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publication status
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Journal of Chemical Physics
volume
123
issue
5
publisher
American Institute of Physics
external identifiers
  • wos:000231168700026
  • scopus:24044554600
ISSN
0021-9606
DOI
10.1063/1.1989319
language
English
LU publication?
yes
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d76322e3-42e7-4aa6-918a-2aa877c67d21 (old id 229657)
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2007-10-05 11:32:38
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@article{d76322e3-42e7-4aa6-918a-2aa877c67d21,
  abstract     = {(H2O)(N) clusters generated in a supersonic expansion source with N similar to 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states-the water dimer and a 20-molecule water cluster-were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.},
  articleno    = {054310},
  author       = {Ohrwall, G and Fink, RF and Tchaplyguine, Maxim and Ojamae, L and Lundwall, M and Marinho, RRT and de Brito, AN and Ristinmaa Sörensen, Stacey and Gisselbrecht, Mathieu and Feifel, R and Rander, T and Lindblad, A and Schulz, Joachim and Saethre, LJ and Mårtensson, Nils and Svensson, S and Bjorneholm, O},
  issn         = {0021-9606},
  language     = {eng},
  number       = {5},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {The electronic structure of free water clusters probed by Auger electron spectroscopy},
  url          = {http://dx.doi.org/10.1063/1.1989319},
  volume       = {123},
  year         = {2005},
}