In:
The Journal of Chemical Physics, AIP Publishing, Vol. 125, No. 8 ( 2006-08-28)
Abstract:
We have studied the structures and stabilities of Al14In− (n=1–11) clusters at the density functional level of theory. The experimentally observed Al14In− (n=3, 5, 7, 9, and 11) [Bergeron et al., Science 307, 231 (2005)] are found to be stable both kinetically and thermodynamically. Al14I3−, not Al14I−, is the first member of the Al14In− series in the mass spectrometric experiment, which is ascribable to the low kinetic stability of the Al14I− cluster. The Al14 core in Al14I3− is close to neutral Al14, both electronically and structurally. Population analysis shows that charge transfer occurs from the Al cluster to the I atoms, where the populations for Al14 vary from −0.70(Al14I−) to +0.96(Al14I11−). The Al14I5− and Al14I7− clusters have the structure of Al14I3− as a core framework, but, for n=9 and 11, we found many more stable isomers than the isomers having the Al14I3− core. In particular, the shape of Al14 in the Al14I11− cluster is a hexagonal wheel-shaped form, which was observed in the x-ray experiment for the metalloid complex [Al14{N(SiMe3)2}6I6Li(OEt2)2] −[Li(OEt2)4]+∙toluene [Köhnlein et al., Angew. Chem., Int. Ed. 39, 799 (2000)] . We have demonstrated that a simple jellium model cannot describe the structure and stability of the iodine-doped aluminum clusters, although it is successful for describing those of aluminum clusters. The electronic and geometric changes of the Al14− cluster due to the presence of iodines are very similar to the case of a magic cluster Al13−. It can be concluded from our electronic and structural analysis that one cannot regard the Al14 core as an alkaline earthlike superatom in the Al14 iodide clusters.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
2006
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
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