Single-Component Molecular Metals as Multiband π-d Systems

Electronic states of single-component molecular metals M(tmdt)2 (M = Ni, Au) are studied theoretically. We construct an effective three-band Hubbard model for each material by numerical fitting to first-principles band calculations, while referring to molecular orbital calculations for the isolated molecules. The model consists of two kinds of base orbital for each molecule with hybridization between them, i.e., a \pi-character orbital for each of the two tmdt ligands, and, a pd\pi-orbital for M = Ni or a pd\sigma-orbital for M = Au centered on the metal site; this indicates that these materials can be considered as novel multiband \pi-d systems. We find that both orbitals contribute to realize the metallic character in Ni(tmdt)2. The origin of the antiferromagnetic transition observed in Au(tmdt)2 is also discussed based on this model.