Assembling nanowires from Mo-S clusters and effects of iodine doping on electronic structure

Using ab initio calculations, we find high stability of octahedral Mo _3nS_3n+2 clusters, which can further be condensed to form Mo3nS3n+2 (n, an integer) nanowires. These linear structures are energetically more favorable compared with other closed-packed polyhedral isomers of Mo-S clusters. The octahedral units in nanowires are stabilized by strong Mo-Mo interactions and p-d hybridization between Mo 4d and S 2p orbitals. There is a free electron-like band that crosses the Fermi energy in infinite nanowires and leads to their metallic character. Iodine doping acts as electron donor and can be used to tailor the electronic conductivity. For Mo₁₂S ₈I₄ nanowires, both electrons and holes are found to contribute to conduction. These nanowires are energetically more favorable than the experimentally obtained Mo₁₂S₆I₁₂ nanowires.