Insertion of transition metal atoms and ions into the nanoscale dodecahedral silsesquioxane (T_12-POSS) cage: Structures, stabilities and electronic properties

摘要

The geometries of the polyhedral oligomeric silsesquioxane (T_12-POSS) cage, (HSiO_3/2)_12, containing the endohedral transition metal atoms or ions: Sc~(0+1,+2), Ti~(0+2), Cr~(0+1,+2), Mn~(0,+1,+2) Fe(0,+1,+2) Co~(0,+1,+2) Ni~(0,+1,+2) Cu~(0,+1,+2) Zn~(0,+1,+2) Mo~0 and W~0,+1,+2) have been optimized at the B3LYP/6-311G(d,p) level of theory. The density functional theory (DFT) calculations predict that all these transition metal species form endohe_dral complexes within the T_12-FOSS cage. The inclusion energies, electronic properties, the HOMO-LUMO gaps, and ionization potentials of these endohedral transition metal T_12-FOSS complexes and their ~31Si and 1Н chemical shifts of (SiH0_3/2)_12 are predicted and discussed.