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Title: Vibrationally specific photoionization cross sections of acrolein leading to the Χ{sup ~}A{sup '} ionic state

The vibrational branching ratios in the photoionization of acrolein for ionization leading to the Χ{sup ~}A{sup '} ion state were studied. Computed logarithmic derivatives of the cross section and the corresponding experimental data derived from measured vibrational branching ratios for several normal modes (ν{sub 9}, ν{sub 10}, ν{sub 11}, and ν{sub 12}) were found to be in relatively good agreement, particularly for the lower half of the 11–100 eV photon energy range considered. Two shape resonances have been found near photon energies of 15.5 and 23 eV in the photoionization cross section and have been demonstrated to originate from the partial cross section of the A{sup ′} scattering symmetry. The wave functions computed at the resonance complex energies are delocalized over the whole molecule. By looking at the dependence of the cross section on the different normal mode displacements together with the wave function at the resonant energy, a qualitative explanation is given for the change of the cross sections with respect to changing geometry.
Authors:
;  [1] ; ; ;  [2] ;  [3]
  1. Department of Chemistry, Texas A and M University, College Station, Texas 77843-3255 (United States)
  2. Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)
  3. Advanced Light Source, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22419858
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 9; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACROLEIN; COMPLEXES; CROSS SECTIONS; EV RANGE; IONS; MOLECULES; PHOTOIONIZATION; PHOTONS; SCATTERING; WAVE FUNCTIONS