Anionic nickel and nitrogen effects in the chiral antiferromagnetic antiperovskite Mn3NiN

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 Gamma(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)(alpha+)B(beta-)X(delta-) 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 Mn3BN compounds, showing that the antiperovskite structure is an ideal platform to encounter negative oxidation states for metals sitting at the corner B-sites.

Automated summary

Magnetic antiperovskites exhibit chiral noncollinear antiferromagnetic ordering and possess remarkable properties such as negative thermal expansion and anomalous Hall effects. However, the electronic structure details related to oxidation states and octahedral center's site effects are still limited. In this study, we investigate the nitrogen site effects on the structural, electronic, magnetic, and topological properties of antiperovskites using theoretical calculations based on density-functional theory. We find that nitrogen vacancy enhances the anomalous Hall conductivity and maintains the chiral Gamma(4g) antiferromagnetic ordering. Additionally, we analyze the oxidation states of Ni- and Mn-sites through Bader charges and electronic structure analysis, revealing negative and positive oxidation states respectively, which is expected in antiperovskites to achieve charge neutrality.