First-principles calculations of inorganic metallocene nanowires

Inspired by the recently synthesized inorganic metallocene derivatives Fe(P4)22−, we have identified four stable inorganic metallocene nanowires, MP4 (M = Sc, Ti, Cr and Fe) in configurations of either regular quadrangular prism (Q-type) or anticube (A-type), and further investigated their magnetic and electronic characteristics utilizing the first-principles calculation. It shows that CrP4 is a ferromagnetic metal, while other nanowires are semiconducting antiferromagnets with bandgaps of 0.44, 1.88, and 2.29 eV within the HSE06 level. It also shows that both ScP4 and TiP4 can be stabilized in the Q-type and A-type, corresponding to the antiferromagnetic and ferromagnetic ground states, respectively, indicating a configuration-dependent magnetism. The thermodynamic and lattice stabilities are confirmed by the ab initio molecular dynamics and phonon spectra. This study has unmasked the structural and physical properties of novel inorganic metallocene nanowires, and revealed their potential application in spintronics.