Title
Bonding study in all-metal clusters containing Al-4 units Bonding study in all-metal clusters containing Al-4 units
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Washington, D.C. ,
Subject
Physics
Chemistry
Source (journal)
The journal of physical chemistry : A : molecules, spectroscopy, kinetics, environment and general theory. - Washington, D.C., 1997, currens
Volume/pages
111(2007) :46 , p. 11885-11893
ISSN
1089-5639
1520-5215
ISI
000250967800020
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
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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