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 MgmAln (-) (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 Mg3Al11 and Mg2Al12 (-), did the aluminum moieties exhibit Zintl anion-like characteristics.
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Haopeng
H
Wang
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Yeon Jae
YJ
Ko
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Xinxing
X
Zhang
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Gerd
G
Gantefoer
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, 76128 Karlsruhe, Germany.
Hansgeorg
H
Schnoeckel
Department of Chemistry, University of Maryland, College Park, Maryland 20742, USA.
Bryan W
BW
Eichhorn
Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
Puru
P
Jena
Department of Chemistry, McNeese State University, Lake Charles, Louisiana 70609, USA.
Boggavarapu
B
Kiran
Department of Physics, West Chester University, West Chester, Pennsylvania 19383, USA.
Anil K
AK
Kandalam
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Kit H
KH
Bowen