Magnetic Ordering in Tetragonal 3d Metal Arsenides M2As (M = Cr, Mn, Fe): An Ab Initio Investigation

作者：Zhang Yuemei; Brgoch Jakoah; Miller Gordon J^*

来源：Inorganic Chemistry, 2013, 52(6): 3013-3021.

DOI：10.1021/ic3024716

The electronic and magnetic structures of the tetragonal Cu2Sb-type 3d metal arsenides (M2As, M = Cr, Mn, Fe) were examined using density functional theory to identify chemical influences on their respective patterns of magnetic order. Each compound adopts a different antiferromagnetic (AFM) ordering of local moments associated with the 3d metal sites, but every one involves a doubled crystallographic c-axis. These AFM ordering patterns are rationalized by the results of VASP calculations on several magnetically ordered models using a x a x 2c supercell. Effective exchange parameters obtained from SPRKKR calculations indicate that both direct and indirect exchange couplings play essential roles in understanding the different magnetic orderings observed. The nature of nearest-neighbor direct exchange couplings, that is, either ferromagnetic (FM) or AFM, were predicted by analysis of the corresponding crystal orbital Hamilton population (COHP) curves obtained by TB-LMTO calculations. Interestingly, the magnetic structures of Fe2As and Mn2As show tetragonal symmetry, but a magnetostrictive tetragonal-to-orthorhombic distortion could occur in Cr2As through AFM Cr1-Cr2 coupling between symmetry inequivalent Cr atoms along the a-axis, but FM coupling along the b-axis. A LSDA+U approach is required to achieve magnetic moment values for Mn2As in better agreement with experimental values, although computations always predict the moment at the M1 site to be lower than that at the M2 site. Finally, a rigid-band model applied to the calculated DOS curve of Mn2As correctly assesses the magnetic ordering patterns in Cr2As and Fe2As.

• 出版日期2013-3-18