Electronic structure and magnetism of equiatomic FeN

Abstract

In order to investigate the phase stability of equiatomic FeN compounds and the structure-dependent magnetic properties, the electronic structure and total energy of FeN with NaCl, ZnS and CsCl structures and various magnetic configurations are calculated using the first-principles TB-LMTO-ASA method. Among all the FeN phases considered, the antiferromagnetic NaCl structure with q=(00pi) is found to have the lowest energy at the theoretical equilibrium volume. However, the FM NaCl phase lies only 1mRyd higher. The estimated equilibrium lattice constant for nonmagnetic ZnS-type FeN agrees quite well with the experimental value, but for the AFM NaCl phase the estimated value is 6.7% smaller than that observed experimentally. For ZnS-type FeN, metastable magnetic states are found for volumes larger than the equilibrium value. On the basis of an analysis of the atom- and orbital-projected density of states and orbital-projected Crystal Orbital Hamilton Population, the iron-nitrogen interactions in NM ZnS, AFM NaCl and FM CsCl structures are discussed. The leading Fe-N interactions is due to the d-p iron-nitrogen hybridization, while considerable s-p and p-p hybridizations are also observed in all three phases. The iron magnetic moment in FeN is found to be highly sensitive to the nearest-neighboring Fe-N distance. In particular, the magnetic moment shows an abrupt drop from a value of about 2 muB to zero with the reduction of the Fe-N distance for the ZnS and CsCl structures.