Anionic nickel and nitrogen effects in the chiral antiferromagnetic antiperovskite Mn 3 NiN.

Magnetic antiperovskites, having chiral noncollinear antiferromagnetic ordering, have shown remarkable properties that range from negative thermal expansion to anomalous Hall effects. Nevertheless, details on the electronic structure, related to the oxidation states and the octahedral center's site effects, are still scarce. Here, we show a theoretical study, based on first-principles calculations in the framework of density-functional theory (DFT), on the electronic properties associated with the nitrogen site effects on the structural, electronic, magnetic, and topological degrees of freedom. Thus, we show that the nitrogen vacancy increases the value of the anomalous Hall conductivity and retains the chiral Γ 4g antiferromagnetic ordering. Moreover, we reveal, based on the Bader charges and the electronic structure analysis, the negative and positive oxidation states of the Ni- and Mn-sites, respectively. This is in agreement with the expected A 3 α + B β - X δ - oxidation states to satisfy charge neutrality in antiperovskites, but the negative charge is rare for transition metals. Finally, we extrapolate our findings on the oxidation states to several Mn 3 BN compounds, showing that the antiperovskite structure is an ideal platform to encounter negative oxidation states for metals sitting at the corner B-sites.