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Photoelectron spectroscopy and theoretical calculations of SO{sub 4}{sup {minus}} and HSO{sub 4}{sup {minus}}: Confirmation of high electron affinities of SO{sub 4} and HSO{sub 4}

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp992726r· OSTI ID:20017558

The authors present a combined photoelectron spectroscopic and theoretical study of SO{sub 4}{sup {minus}} and HSO{sub 4}{sup {minus}} and their corresponding neutral species in the gas phase. Very high electron affinities were measured for SO{sub 4} and HSO{sub 4}, which are 5.10(0.10) and 4.75(0.10) eV, respectively. Theoretical calculations of the neutral and anionic species using both density functional and ab initio molecular orbital theory confirm the high electron affinities of the two species. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. Both SO{sub 4}{sup {minus}} and SO{sub 4} have C{sub 2{nu}} symmetry, whereas both HSO{sub 4}{sup {minus}} and HSO{sub 4} have C{sub s} symmetry. Significant geometry changes are predicted between the equilibrium geometries of the anion species and the neutral species for both systems that are consistent with the broad nature of the measured photoelectron spectra.

Research Organization:
Washington State Univ., Richland, WA (US)
Sponsoring Organization:
US Department of Energy
OSTI ID:
20017558
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 3 Vol. 104; ISSN 1089-5639; ISSN JPCAFH
Country of Publication:
United States
Language:
English

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