Photodetachment, photofragmentation, and fragment autodetachment of [O 2n(H2 O) m] - Clusters: Core-anion structures and fragment energy partitioning

Daniel J. Goebbert, Andrei M Sanov

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Abstract

Building on the past studies of the O 2n- and O 2- (H2 O) m cluster anion series, we assess the effect of the strong hydration interactions on the oxygen-core clusters using photoelectron imaging and photofragment mass spectroscopy of [O2n (H2 O) m]- (n=1-4, m=0-3) at 355 nm. The results show that both pure-oxygen and hydrated clusters with n≥2 form an O4- core anion, indicated in the past work on the pure-oxygen clusters. All clusters studied can be therefore described in terms of O4- (H2 O) m (O2) n-2 structures, although the O4- core may be strongly perturbed by hydration in some of these clusters. Fragmentation of these clusters yields predominantly O2- and O 2- (H2 O) l (l<m) anionic products. The low-electron kinetic energy O O2- autodetachment features, prominent in the photoelectron images, signal that the fragments are vibrationally excited. The relative intensity of photoelectrons arising from O O2- fragment autodetachment is used to shed light on the varying degree of fragment excitation resulting from the cluster fragmentation process depending on the solvent conditions.

Original languageEnglish (US)
Article number104308
JournalThe Journal of Chemical Physics
Volume131
Issue number10
DOIs
StatePublished - 2009

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photodetachment
Photoelectrons
Anions
fragments
Oxygen
anions
Hydration
Kinetic energy
photoelectrons
energy
Spectroscopy
hydration
Imaging techniques
fragmentation
oxygen
Electrons
mass spectroscopy
kinetic energy
products

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Photodetachment, photofragmentation, and fragment autodetachment of [O 2n(H2 O) m] - Clusters: Core-anion structures and fragment energy partitioning",
abstract = "Building on the past studies of the O 2n- and O 2- (H2 O) m cluster anion series, we assess the effect of the strong hydration interactions on the oxygen-core clusters using photoelectron imaging and photofragment mass spectroscopy of [O2n (H2 O) m]- (n=1-4, m=0-3) at 355 nm. The results show that both pure-oxygen and hydrated clusters with n≥2 form an O4- core anion, indicated in the past work on the pure-oxygen clusters. All clusters studied can be therefore described in terms of O4- (H2 O) m (O2) n-2 structures, although the O4- core may be strongly perturbed by hydration in some of these clusters. Fragmentation of these clusters yields predominantly O2- and O 2- (H2 O) l (l2- autodetachment features, prominent in the photoelectron images, signal that the fragments are vibrationally excited. The relative intensity of photoelectrons arising from O O2- fragment autodetachment is used to shed light on the varying degree of fragment excitation resulting from the cluster fragmentation process depending on the solvent conditions.",
author = "Goebbert, {Daniel J.} and Sanov, {Andrei M}",
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AU - Goebbert, Daniel J.

AU - Sanov, Andrei M

PY - 2009

Y1 - 2009

N2 - Building on the past studies of the O 2n- and O 2- (H2 O) m cluster anion series, we assess the effect of the strong hydration interactions on the oxygen-core clusters using photoelectron imaging and photofragment mass spectroscopy of [O2n (H2 O) m]- (n=1-4, m=0-3) at 355 nm. The results show that both pure-oxygen and hydrated clusters with n≥2 form an O4- core anion, indicated in the past work on the pure-oxygen clusters. All clusters studied can be therefore described in terms of O4- (H2 O) m (O2) n-2 structures, although the O4- core may be strongly perturbed by hydration in some of these clusters. Fragmentation of these clusters yields predominantly O2- and O 2- (H2 O) l (l2- autodetachment features, prominent in the photoelectron images, signal that the fragments are vibrationally excited. The relative intensity of photoelectrons arising from O O2- fragment autodetachment is used to shed light on the varying degree of fragment excitation resulting from the cluster fragmentation process depending on the solvent conditions.

AB - Building on the past studies of the O 2n- and O 2- (H2 O) m cluster anion series, we assess the effect of the strong hydration interactions on the oxygen-core clusters using photoelectron imaging and photofragment mass spectroscopy of [O2n (H2 O) m]- (n=1-4, m=0-3) at 355 nm. The results show that both pure-oxygen and hydrated clusters with n≥2 form an O4- core anion, indicated in the past work on the pure-oxygen clusters. All clusters studied can be therefore described in terms of O4- (H2 O) m (O2) n-2 structures, although the O4- core may be strongly perturbed by hydration in some of these clusters. Fragmentation of these clusters yields predominantly O2- and O 2- (H2 O) l (l2- autodetachment features, prominent in the photoelectron images, signal that the fragments are vibrationally excited. The relative intensity of photoelectrons arising from O O2- fragment autodetachment is used to shed light on the varying degree of fragment excitation resulting from the cluster fragmentation process depending on the solvent conditions.

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