A theoretical study of isomerism in doped aluminum MAl12 and MAl12X12 clusters with 40 and 50 valence electrons

Abstract

Systematic density functional B3LYP calculations with the 6-31G* and 6-311+G* basis sets have been employed in order to investigate the structure, vibrational frequencies, relative energies, vertical ionization potentials, and magnetic shielding constants of endohedral and exohedral isomers in two related families of doped aluminum MAl₁₂ and alane MAl₁₂H₁₂ clusters with 40 and 50 valence electrons, respectively. Isomerization barriers have been also determined. Trends in these properties with changing heteroatom M in various series have been followed. The similarities and differences between the aluminides and alanes as well as between the alanes MAl₁₂H₁₂ and related boranes MB₁₂H₁₂ and gallanes MGa₁₂H₁₂ have been scrutinized.