Evidence for the direct population of solid-state bands by non-bonding electron pairs in compounds of the type CsM II X3(M II = Ge, Sn, Pb; X = Cl, Br, I)

Abstract

The optical and electrical conductivity behaviour of phases in the systems CsMIIX3(MII= Ge, Sn, Pb; X = Cl, Br, I) are explained by donation of electron density from non-bonding electron pairs on the MII metal into a conduction band formed by the overlap of halogen d states. The greater ionic character of the PbII reduces the electron density donation and dominates the optical spectra fo the Pb-rich phases. The optical properties of the CsMIII3 phases (MII= Ge, Sn, Pb) show that the donation of non-bonding electron-pair electrons to iodine d bands is favoured over the self-population of the bands by iodine electrons. Mossbauer data for the mixed systems CsSn1 –xPbxX3(X = Br,I) and CsSn1 –xCdxBr3 are consistent with the band structure properties for these phases.