O'Donnell Shaun, Mahatara Sharad, Lany Stephan, Bauers Sage R, Smaha Rebecca W, Neilson James R
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1877, United States.
National Renewable Energy Laboratory, Golden, Colorado 80401, United States.
Inorg Chem. 2024 Aug 26;63(34):16075-16080. doi: 10.1021/acs.inorgchem.4c02693. Epub 2024 Aug 14.
We investigate the synthesis of antiperovskite "MnAlN" using the published synthesis procedure, as well as several new reaction pathways. In each case, only a combination of antiperovskite MnN and MnAl or precursors is obtained. The identity of the obtained antiperovskite phase is unambiguously determined to be MnN via synchrotron powder X-ray diffraction (SPXRD), X-ray absorption spectroscopy (XAS), and magnetometry. The experimental results are further supported by thermochemical calculations informed by density functional theory (DFT), which find MnAlN to be metastable versus decomposition into Mn and AlN. The DFT-based calculations also predict an antiferromagnetic ground state for MnAlN. This directly contradicts the previously reported ferromagnetic behavior of "MnAlN". Instead, the observed magnetic behavior is consistent with ferrimagnetic MnN. We examine the data in the original publication and conclude that the compound reported to be MnAlN is in fact MnN.
我们采用已发表的合成方法以及几种新的反应途径研究了反钙钛矿“MnAlN”的合成。在每种情况下，仅得到了反钙钛矿MnN与MnAl或前驱体的组合。通过同步辐射粉末X射线衍射（SPXRD）、X射线吸收光谱（XAS）和磁学测量，明确确定所获得的反钙钛矿相为MnN。密度泛函理论（DFT）提供的热化学计算进一步支持了实验结果，该计算发现MnAlN相对于分解为Mn和AlN是亚稳态的。基于DFT的计算还预测MnAlN具有反铁磁基态。这直接与先前报道的“MnAlN”的铁磁行为相矛盾。相反，观察到的磁行为与亚铁磁性的MnN一致。我们检查了原始出版物中的数据，并得出结论，报道为MnAlN的化合物实际上是MnN。
