Abstract
We perform a systematic study of electronic structures based on the ab initio calculations for single component molecular metals, Ni(tmdt)2, Au(tmdt)2, Au(tmstfdt)2, Cu(dmdt)2, and Zn(tmdt)2. First, we discuss the central metal dependence of the character of states around highest occupied molecular orbital (HOMO) [or singly occupied molecular orbital (SOMO)] and lowest unoccupied molecular orbital (LUMO) for isolated molecules and show that the stable structure of each isolated molecule is properly predicted. For solid state of Ni(tmdt)2, Au(tmdt)2, and Au(tmstfdt)2, the molecular shape is planar and the HOMO–LUMO separation in the Ni complex or the (HOMO−1)–SOMO separation in the Au complexes is smaller than the inter-molecular interaction, which leads to the metallic state of Ni(tmdt)2 and a unique antiferromagnetic state of Au(tmdt)2. For Cu(dmdt)2 and Zn(tmdt)2, their two intra-molecular lingands are strongly twisted. Theoretically we obtain a stable antiferromagnetic solution for the solid state of the Cu complex. The theoretical electronic structures of solid phases of the Cu complex and Zn complex are compared with available experimental information.
