Tuning of metal-metal bonding by counterion size in hypothetical AeTiO(2) compounds.
In a theoretical study of a "defect perovskite" structure of stoichiometry AeTiO(2) (AE = alkaline earth metal, Be, Mg, Ca, Sr, and Ba), we find substantial Ti-Ti bonding tuned by the size of the Ae(2+) cation. The bonding is one-dimensional, partially sigma, partially pi. These formal d(2) systems are expected to be nonmagnetic and metallic. A competing (for same Ae) structural alternative, an ordered rock-salt structure, is magnetic.
Wen
Xiao-Dong
XD
Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, USA.
Cahill
Thomas J
TJ
Hoffmann
Roald
R
Miura
Akira
A