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

F. Ahu Akin; Laura K. Schirra; Andrei Sanov

doi:10.1021/jp062135i

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

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

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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.

Original language	English (US)
Pages (from-to)	8031-8036
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	110
Issue number	26
DOIs	https://doi.org/10.1021/jp062135i
State	Published - Jul 6 2006

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Physical and Theoretical Chemistry

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@article{37c8aa745e5c44c78d659277bc02cc58,

title = "Photoelectron imaging study of the effect of monohydration on O 2 - photodetachment",

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.",

author = "{Ahu Akin}, F. and Schirra, {Laura K.} and Andrei Sanov",

year = "2006",

month = jul,

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doi = "10.1021/jp062135i",

language = "English (US)",

volume = "110",

pages = "8031--8036",

journal = "Journal of Physical Chemistry A",

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T1 - Photoelectron imaging study of the effect of monohydration on O 2 - photodetachment

AU - Ahu Akin, F.

AU - Schirra, Laura K.

AU - Sanov, Andrei

PY - 2006/7/6

Y1 - 2006/7/6

N2 - 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.

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

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