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Al3Oy (y=0–5) clusters: Sequential oxidation, metal-to-oxide transformation, and photoisomerization

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.476583· OSTI ID:1490326
 [1];  [1];  [1];  [1];  [1]
  1. Washington State Univ., Richland, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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Here, photoelectron spectra of a series of Al3O$$\overline{y}$$ clusters (y=0–5) are presented at several photon energies: 532, 355, 266, and 193 nm. The electron affinities and low-lying electronic states of the Al3Oy clusters are reported. The photoelectron spectra clearly reveal a sequential oxidation behavior and how the electronic structure of the clusters evolves from that of a metal cluster at Al3 to that of a complete oxide cluster at Al3O5: Two valence electrons of Al3 are observed to be transferred to each additional O atom until Al3O5, where all the nine valence electrons of Al3 are transferred to the five O atoms. The anion, Al3O$$-\atop{5}$$, which can be viewed as (Al3+)3(O2-)5, is found to be a closed shell cluster, yielding an extremely high electron affinity for Al3O5 (4.92 eV). The electron affinities of the remaining clusters are: 1.90 (Al3), 1.57 eV (Al3O), 2.18 eV (Al3O2), 2.80 eV (Al3O3), and 3.58 eV (Al3O4). An electronic excited state of Al$$-\atop{3}$$ is also observed at 0.40 eV above the Al$$-\atop{3}$$ ground state. Isomers are observed for all the oxide clusters with lower electron affinities. Particularly, vibrational structures are observed for the two isomers of Al3O$$-\atop{3}$$, as well as a photoisomerization process between the two isomers. Lastly, the structure and bonding of the oxide clusters are discussed based on the experimental data and the known structures for Al3 and Al3O.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1490326
Alternate ID(s):
OSTI ID: 636143
Report Number(s):
PNNL-SA--29725
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 109; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

An efficient, renormalized self-energy for calculating the electron binding energies of closed-shell molecules and anions journal January 2005
Structure characterization of metal oxide clusters by vibrational spectroscopy: possibilities and prospects journal January 2012
A photoelectron spectroscopy and quantum chemical study on ternary Al–B–O clusters: Al n BO 2 − and Al n BO 2 ( n = 2, 3) journal January 2018
Structural and bonding properties of Cu 3 O 3 − and Cu 3 O 4 − clusters: anion photoelectron spectroscopy and density functional calculations journal January 2018
Photoelectron spectra of Al 2 O 2 − and Al 3 O 3 − via slow electron velocity-map imaging journal January 2019
Combined experimental and theoretical study of small aluminum oxygen clusters journal October 2007

Figures / Tables (13)

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Table I(p. 5)table Table I
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Table II(p. 6)table Table II
Figure 10(p. 7)figure Figure 10
Figure 11(p. 10)figure Figure 11

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Photoelectron Spectra
general oxide
oxide