Semiempirical band structure calculations on skutterudite-type compounds

Semiempirical band structure calculations were performed on several skutterudite-type compounds by using the extended Hückel method. Starting with the molecular orbital calculations on isolated P4 and As4 rings, the reason for the band dispersions of the skutterudites was found to be the interactions between the nonmetal atoms. Both the intermolecular and the intramolecular interactions between the phosphorus atoms are stronger than those between the arsenic atoms. Hence, the dispersion of the bands in CoP3 is larger than that in CoAs3. The COOP (crystal orbital overlap population) integrals of the intramolecular P-P bonds reveal the relation between the valence electron count and the observed bond lengths. The P-P bonds in the skutterudite-type compounds like TP3 (T = Co, Rh, Ir) become stronger by reduction as in NiP3 and weaker by oxidation as in RT4X12 (X = P, As, Sb; R = alkaline earth or rare earth metals) because the bands near the Fermi level are bonding. The electronic reason for the geometric distortion of the Ge2Y2 (Y = S, Se) units of mixed skutterudites TGe1.5Y1.5 is caused by an electron pair gap on germanium, which corresponds to low electron density perpendicular to the ring plane on the germanium atoms.