First-principles study of one-dimensional sandwich wires [(P)₅TM]∞ (TM = Ti, V, Cr, Mn, Fe, Co)

Since the discovery of ferrocene, many one-dimensional metallic sandwich molecular wires have been identified. However, most of the known systems are assembled from organic molecules. Suffering from many drawbacks has, however, hampered their widespread applications. With the goal of breaking this logjam, we provide a blueprint for the designing of a variety of novel sandwich molecular wires ([(P)5TM]∞, TM = Ti, V, Cr, Mn, Fe, and Co) assembled from ferrocene-like inorganic molecules (P)5TM, offering evidence of the existence of inorganic molecular wires in this class. We present first-principles calculations to investigate systematically the electronic and magnetic properties of such novel inorganic sandwich molecular wires. Compared with the organic molecular wires, all the inorganic [(P)5TM]∞ wires are of large magnetic moment. Among them, we find that [(P)5V]∞, [(P)5Cr]∞ and [(P)5Mn]∞ display ferromagnetic character, while for [(P)5Ti]∞, [(P)5Fe]∞ and [(P)5Co]∞, the magnetic coupling is antiferromagnetic. More remarkably, the TM atoms distributed in these wires show regular docking and lead to structures with ordered spin signals, which is a long-term dream of spintronics. We propose that the difference in magnetic coupling for the studied systems is related to the competition between two exchange interactions of TM atoms. Specifically, we propound that the general mechanism for the formation of stable 1D [(P)5TM]∞ involves the transfer of one electron from the TM atom to the P5 ligand forming [Formula: see text] and TM(+) alternating structure.