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Title: The viability of aluminum Zintl anion moieties within magnesium-aluminum clusters

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have investigated the extent to which the aluminum moieties within selected magnesium-aluminum clusters are Zintl anions. Magnesium-aluminum cluster anions were generated in a pulsed arc discharge source. After mass selection, photoelectron spectra of Mg{sub m}Al{sub n}{sup −} (m, n = 1,6; 2,5; 2,12; and 3,11) were measured by a magnetic bottle, electron energy analyzer. Calculations on these four stoichiometries provided geometric structures and full charge analyses for the cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra). Calculations revealed that, unlike the cases of recently reported sodium-aluminum clusters, the formation of aluminum Zintl anion moieties within magnesium-aluminum clusters was limited in most cases by weak charge transfer between the magnesium atoms and their aluminum cluster moieties. Only in cases of high magnesium content, e.g., in Mg{sub 3}Al{sub 11} and Mg{sub 2}Al{sub 12}{sup −}, did the aluminum moieties exhibit Zintl anion-like characteristics.
Authors:
; ; ; ;  [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [6]
  1. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States)
  2. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, 76128 Karlsruhe (Germany)
  3. Department of Chemistry, University of Maryland, College Park, Maryland 20742 (United States)
  4. Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284 (United States)
  5. Department of Chemistry, McNeese State University, Lake Charles, Louisiana 70609 (United States)
  6. Department of Physics, West Chester University, West Chester, Pennsylvania 19383 (United States)
Publication Date:
OSTI Identifier:
22253402
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM; ANIONS; DENSITY FUNCTIONAL METHOD; MAGNESIUM; PHOTOELECTRON SPECTROSCOPY; PULSES; SODIUM; SPECTRA