Max-Planck-Institut für Festkörperforschung, Heisenbergstr. 1, 70569 Stuttgart, Germany.
Chem Asian J. 2013 Apr;8(4):743-54. doi: 10.1002/asia.201200794. Epub 2013 Jan 21.
Metal-pernitride compounds belong to a class of chemical systems in which both the complex ions and the non-bonding electrons may play roles in the formation of their modified crystalline structures. To investigate this issue, the energy landscapes of pernitrides of metals with different maximum valence (M=Ca, Sr, Ba, La, and Ti) were globally explored on the ab initio level at standard and high pressures, thereby yielding possible (meta)stable modifications in these systems together with information on how the landscape changed as function of the valence of the metal cation. For all of the systems in which no compounds had been synthesized so far, we predicted the existence of kinetically stable modifications that should, in principle, be experimentally accessible. In particular, TiN2 should crystallize in a new structure type, TiN2-I.
金属氮化物化合物属于一类化学体系，其中复杂离子和非键电子都可能在其改性晶体结构的形成中发挥作用。为了研究这个问题，我们在标准和高压条件下，从第一性原理的角度对具有不同最大价态的金属（M=Ca、Sr、Ba、La 和 Ti）的过氮化物的能区进行了全局探索，从而得到了这些体系中可能存在的（亚稳）稳定修饰体，以及能区如何随金属阳离子价态变化的信息。对于迄今为止尚未合成化合物的所有体系，我们预测了动力学稳定修饰体的存在，原则上这些修饰体应该是可以通过实验得到的。特别是 TiN2 应该会结晶成一种新的结构类型 TiN2-I。
