Abstract
The changes in electronic structure of the tetracyanoplatinate complex accompanying the transition [Pt(CN)
2−
4]
n
(insulator) + oxidant → [Pt(CN)
2 −
q+
4]
n
(conductor) have been investigated with a cluster model approach. Calculations for trimer (
n = 3) cluster models of the insulator and conductor have been performed with the self-consistent-field Xα Dirac scattered-wave method. Based on the cluster electronic structure, we infer that the valence band edge in the insulator is not d
zz like, but consists of metal (dδ + dπ) and ligand character. Partial oxidation of this band results in a shortening of the inter-stack distance, leading in turn to a partially occupied d
zz-like valence band. Thus electron transport occurs along the Pt backbone.