Theoretical study of the structural and electronic properties of aggregates, wires, and bulk phases formed from M@Si 16 superatoms (M = Sc − , Ti, V + )

Starting with the nearly spherical endohedral M@Si 16 cage‐like clusters (M = Sc − , Ti, V + ) in their fullerene‐like isomerical form with D 4 d symmetry, we study the trends in the formation of [Ti@Si 16 ] n , [Sc@Si 16 K] n , and [V@Si 16 F] n aggregates as their size increase ( n ≤ 9). We identify specially stable linear, planar, and three‐dimensional patterns, which can serve to grow low‐dimensional infinite systems. The structure and cohesive energy of a few infinite chains of that type are optimized. We also present calculations of fcc, bcc, and single cubic crystal meta stable phases having the Ti@Si 16 superatom as basic unit, as well as cubic NaCl and CsCl bulk structures of Sc@Si 16 K and V@Si 16 F supermolecules. The orientation and isomerization of the superatom or supermolecule in the cubic cell plays an important role. The projected density of states of V@Si 16 F crystal with NaCl structure shows a meta stable ferromagnetic phase due to polarization of d electrons of vanadium. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011