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Title
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Bonding study in all-metal clusters containing Al-4 units
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Author
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Abstract
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| The nature of the bonding of a series of gas-phase all-metal clusters containing the Al-4 unit attached to an alkaline, alkaline earth, or transition metal is investigated at the DFT level using Mulliken, quantum theory of atoms in molecules (QTAIM), and Hirshfeld iterative (Hirshfeld-I) atomic partitionings. The characterization of ionic, covalent, and metallic bonds is done by means of charge polarization and multicenter electron delocalization. This Article uses for the first time Hirshfeld-I multicenter indices as well as Hirshfeld-I based atomic energy calculations. The QTAIM charges are in line with the electronegativity scale, whereas Hirshfeld-I calculations display deviations for transition metal clusters. The Mulliken charges fail to represent the charge polarization in alkaline metal clusters. The large ionic character of Li-Al and Na-Al bonds results in weak covalent bonds. On the contrary, scarcely ionic bonds (Be-Al, Cu-Al and Zn-Al) display stronger covalent bonds. These findings are in line with the topology of the electron density. The metallic character of these clusters is reflected in large 3-, 4- and 5-center electron delocalization, which is found for all the molecular fragments using the three atomic definitions. The previously reported magnetic inactivity (based on means of magnetic ring currents) of the 7 system in the Al-4(2-) cluster contrasts with its large pi electron delocalization. However, it is shown that the different results not necessary contradict each other. |
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Language
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English
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Source (journal)
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The journal of physical chemistry : A : molecules, spectroscopy, kinetics, environment and general theory. - Washington, D.C., 1997, currens
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Publication
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Washington, D.C.
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2007
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ISSN
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1089-5639
[print]
1520-5215
[online]
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DOI
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10.1021/JP074973Y
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Volume/pages
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111
:46
(2007)
, p. 11885-11893
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ISI
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000250967800020
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Full text (Publisher's DOI)
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