Bonds, bands, and band gaps in tetrahedrally bonded ternary compounds: The role of group V lone pairs

An interesting class of tetrahedrally coordinated ternary compounds has attracted considerable interest because of their potential as good thermoelectrics. These compounds, denoted as I3-V-VI4, contain three monovalent-I (Cu, Ag), one nominally pentavalent-V (P, As, Sb, Bi), and four hexavalent-VI (S, Se, Te) atoms; and can be visualized as ternary derivatives of the II-VI zincblende or wurtzite semiconductors, obtained by starting from four unit cells of (II-VI) and replacing four type II atoms by three type I and one type V atoms. We find that nominally pentavalent-V atoms are effectively trivalent and their lone (ns2) pairs play an active role in opening up a gap. The lowest conduction band is a strongly hybridized anti-bonding combination of the lone pair and chalcogen (VI) p-states. The magnitude of the gap is sensitive to the nature of the exchange interaction (local vs non-local) and the V-VI distance. We also find that the electronic structure near the gap can be reproduced extremely well within a local theory if one can manipulate the position of the filled d bands of Cu and Ag by an effectively large U.