Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52056 Aachen, Germany.
J Comput Chem. 2012 Oct 5;33(26):2102-7. doi: 10.1002/jcc.23046. Epub 2012 Jun 14.
A metastable bixbyite-type polymorph of vanadium sesquioxide, V(2)O(3), has recently been synthesized, and it transforms to the corundum-type phase at temperatures around 550 °C. The possibility of a paramagnetic to canted antiferromagnetic or even spin-glass-like transition has been discussed. Quantum-chemical calculations on the density-functional theory level including explicit electronic correlation confirm the metastability as well as the semiconducting behavior of the material and predict that the bixbyite-type structure is about 0.1 eV less stable than the well-known corundum-type phase. Nonetheless, quasiharmonic phonon calculations manifest that bixbyite-type vanadium sesquioxide is a dynamically stable compound. Other possible V(2)O(3) polymorphs are shown to be even less suitable candidates for the composition V(2)O(3).
一种亚稳态的三氧化二钒的方铁矿型多晶型物最近被合成出来，其在约 550°C 的温度下转变为刚玉型相。已经讨论了顺磁到倾斜反铁磁甚至自旋玻璃样转变的可能性。在包括显式电子相关的密度泛函理论水平上的量子化学计算证实了该物质的亚稳性和半导体行为，并预测方铁矿型结构比著名的刚玉型相约低 0.1 eV 稳定。尽管如此，准谐声子计算表明，方铁矿型三氧化二钒是一种动力学稳定的化合物。其他可能的 V2O3 多晶型物被证明是更不适合组成 V2O3 的候选物。
