Structural, electronic, and magnetic properties of 3d transition metal monatomic chains: First-principles calculations

In this paper we investigated structural, electronic, and magnetic properties of 3d (light) transition metal atomic chains using first-principles pseudopotential plane-wave calculations. Infinite periodic linear, dimerized linear, and planar zigzag chain structures, as well as their short segments consisting of finite number of atoms have been considered. Like Cu, the periodic, linear chains of Mn, Co, and Ni correspond to a local shallow minimum. However, for most of the infinite periodic chains, neither linear nor dimerized linear structures are favored; to lower their energy the chains undergo a structural transformation to form planar zigzag and dimerized zigzag geometries. Dimerization in both infinite and finite chains is much stronger than the usual Peierls distortion and appears to depend on the number of 3d electrons. As a result of dimerization, a significant energy lowering occurs which, in turn, influences the stability and physical properties. Metallic linear chain of vanadium becomes half-metallic upon dimerization. Infinite linear chain of scandium also becomes half-metallic upon transformation to the zigzag structure. An interplay between the magnetic ground state and the atomic as well as the electronic structure of the chain has been revealed. The end effects influence the geometry, the energetics, and the magnetic ground state of the finite chains. Structure optimization performed using noncollinear approximation indicates significant differences from the collinear approximation. Variation of the cohesive energy of infinite- and finite-size chains with respect to the number of 3d electrons is found to mimic the well-known bulk behavior. The spin-orbit coupling of finite chains is found to be negligibly small. © 2008 The American Physical Society