Photoelectron imaging study of the effect of monohydration on O 2 - photodetachment

F. Ahu Akin, Laura K. Schirra, Andrei M Sanov

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The photodetachment of the O 2 -·H 2O cluster anion at 780 and 390 nm is investigated in comparison with O 2 - using photoelectron imaging spectroscopy. Despite the pronounced shift in the photoelectron spectra, the monohydration has little effect on the photoelectron angular distributions: for a given wavelength and electron kinetic energy (eKE) range, the O 2 -·H 2O angular distributions are quantitatively similar to those for bare O 2 -. This observation confirms that the excess electron in O 2 -·H 2O retains the overall character of the 2pπ g* HOMO of O 2 -. The presence of H 2O does not affect significantly the partial wave composition of the photodetached electrons at a given eKE. An exception is observed for slow electrons, where O 2 -·H 2O exhibits a faster rise in the photodetachment signal with increasing eKE, as compared to O 2 -. The possible causes of this anomaly are (i) the long-range charge-dipole interaction between the departing electron and the neutral O 2·H 2O skeleton affecting the slow-electron dynamics; and (ii) the s wave contributions to the photodetachment, which are dipole-forbidden for π g -1 transitions in O 2 -, but formally allowed in O 2 -·H 2O due to lower symmetry of the cluster anion and the corresponding HOMO.

Original languageEnglish (US)
Pages (from-to)8031-8036
Number of pages6
JournalJournal of Physical Chemistry A
Volume110
Issue number26
DOIs
StatePublished - Jul 6 2006

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photodetachment
Photoelectrons
photoelectrons
Imaging techniques
Electrons
electrons
Kinetic energy
Angular distribution
kinetic energy
Anions
angular distribution
dipoles
anions
musculoskeletal system
Spectroscopy
anomalies
Wavelength
causes
shift
symmetry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Photoelectron imaging study of the effect of monohydration on O 2 - photodetachment. / Ahu Akin, F.; Schirra, Laura K.; Sanov, Andrei M.

In: Journal of Physical Chemistry A, Vol. 110, No. 26, 06.07.2006, p. 8031-8036.

Research output: Contribution to journalArticle

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abstract = "The photodetachment of the O 2 -·H 2O cluster anion at 780 and 390 nm is investigated in comparison with O 2 - using photoelectron imaging spectroscopy. Despite the pronounced shift in the photoelectron spectra, the monohydration has little effect on the photoelectron angular distributions: for a given wavelength and electron kinetic energy (eKE) range, the O 2 -·H 2O angular distributions are quantitatively similar to those for bare O 2 -. This observation confirms that the excess electron in O 2 -·H 2O retains the overall character of the 2pπ g* HOMO of O 2 -. The presence of H 2O does not affect significantly the partial wave composition of the photodetached electrons at a given eKE. An exception is observed for slow electrons, where O 2 -·H 2O exhibits a faster rise in the photodetachment signal with increasing eKE, as compared to O 2 -. The possible causes of this anomaly are (i) the long-range charge-dipole interaction between the departing electron and the neutral O 2·H 2O skeleton affecting the slow-electron dynamics; and (ii) the s wave contributions to the photodetachment, which are dipole-forbidden for π g -1 transitions in O 2 -, but formally allowed in O 2 -·H 2O due to lower symmetry of the cluster anion and the corresponding HOMO.",
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AB - The photodetachment of the O 2 -·H 2O cluster anion at 780 and 390 nm is investigated in comparison with O 2 - using photoelectron imaging spectroscopy. Despite the pronounced shift in the photoelectron spectra, the monohydration has little effect on the photoelectron angular distributions: for a given wavelength and electron kinetic energy (eKE) range, the O 2 -·H 2O angular distributions are quantitatively similar to those for bare O 2 -. This observation confirms that the excess electron in O 2 -·H 2O retains the overall character of the 2pπ g* HOMO of O 2 -. The presence of H 2O does not affect significantly the partial wave composition of the photodetached electrons at a given eKE. An exception is observed for slow electrons, where O 2 -·H 2O exhibits a faster rise in the photodetachment signal with increasing eKE, as compared to O 2 -. The possible causes of this anomaly are (i) the long-range charge-dipole interaction between the departing electron and the neutral O 2·H 2O skeleton affecting the slow-electron dynamics; and (ii) the s wave contributions to the photodetachment, which are dipole-forbidden for π g -1 transitions in O 2 -, but formally allowed in O 2 -·H 2O due to lower symmetry of the cluster anion and the corresponding HOMO.

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