Structure and stability of the Al14 halides Al 14in- (n=1-11): Can we regard the Al 14 core as an alkaline earthlike superatom?

Young Kyu Han, Jaehoon Jung

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Abstract

We have studied the structures and stabilities of Al14I n- (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. Al14I 3-, 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 Al 14I- cluster. The Al14 core in Al 14I3- 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 Al 14 vary from -0.70(Al14I-) to +0.96(Al 14I11-). 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 Al 14- 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.

Original languageEnglish
Article number084101
JournalJournal of Chemical Physics
Volume125
Issue number8
DOIs
StatePublished - 2006

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