Structure and stability of the Al14 halides Al14In - (n=1-11): can we regard the Al14 core as an alkaline earthlike superatom?

We have studied the structures and stabilities of Al(14)I(n) (-) (n=1-11) clusters at the density functional level of theory. The experimentally observed Al(14)I(n) (-) (n=3, 5, 7, 9, and 11) [Bergeron et al., Science 307, 231 (2005)] are found to be stable both kinetically and thermodynamically. Al(14)I(3) (-), not Al(14)I(-), is the first member of the Al(14)I(n) (-) series in the mass spectrometric experiment, which is ascribable to the low kinetic stability of the Al(14)I(-) cluster. The Al(14) core in Al(14)I(3) (-) is close to neutral Al(14), 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(Al(14)I(-)) to +0.96(Al(14)I(11) (-)). The Al(14)I(5) (-) and Al(14)I(7) (-) clusters have the structure of Al(14)I(3) (-) as a core framework, but, for n=9 and 11, we found many more stable isomers than the isomers having the Al(14)I(3) (-) core. In particular, the shape of Al(14) in the Al(14)I(11) (-) cluster is a hexagonal wheel-shaped form, which was observed in the x-ray experiment for the metalloid complex Al(14){N(SiMe(3))(2)}(6)I(6)Li(OEt(2))(2)Li(OEt(2))(4)toluene [Kohnlein 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 Al(13) (-). It can be concluded from our electronic and structural analysis that one cannot regard the Al(14) core as an alkaline earthlike superatom in the Al(14) iodide clusters.