Prediction of ground-state structures and order-disorder phase transitions in II-III spinel oxides: A combined cluster-expansion method and first-principles study
Prediction of ground-state structures and order-disorder phase transitions in II-III spinel oxides: A combined cluster-expansion method and first-principles study
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DOI：
10.1103/physrevb.73.184117
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发表时间：
2006-05
影响因子：
3.7
通讯作者：
Atsuto Seko;Koretaka Yuge;F. Oba;A. Kuwabara;I. Tanaka
中科院分区：
文献类型：
--
作者：
Atsuto Seko;Koretaka Yuge;F. Oba;A. Kuwabara;I. Tanaka
用团簇展开方法和第一性原理计算相结合的方法预测了6个II-III尖晶石氧化物的基态结构。$\mathrm{Mg}{\mathrm{Ga}}_{2}{\mathrm{O}}_{4}$和$\mathrm{Mg}{\mathrm{In}}_{2}{\mathrm{O}}_{4}$的基态是四方晶格的反尖晶石，而$\mathrm{Mg}{\mathrm{Al}}_{2}{\mathrm{O}}_{4}$，的基态是具有四方晶格的反尖晶石$\mathrm{Zn}{\mathrm{Al}}_{2}{\mathrm{O}}_{4}$，$\mathrm{Zn}{\mathrm{Ga}}_{2}{\mathrm{O}}_{4}$，和$\mathrm{Zn}{\mathrm{In}}_{2}{\mathrm{O}}_{4}$是具有立方晶格的普通尖晶石。用蒙特卡罗模拟研究了有序-无序相变行为。通常认为，交换八面体和四面体阳离子的有序-无序转变是发生的。在反尖晶石中，可以识别到一种新的八面体位置上交换II和III阳离子的转变，这在实验上还没有报道。计算了它们的转变温度。
Ground-state structures of six II-III spinel oxides are predicted by combining the cluster expansion method and first principles calculations. The ground states of $\mathrm{Mg}{\mathrm{Ga}}_{2}{\mathrm{O}}_{4}$ and $\mathrm{Mg}{\mathrm{In}}_{2}{\mathrm{O}}_{4}$ are found to be inverse spinels with a tetragonal lattice, whereas those of $\mathrm{Mg}{\mathrm{Al}}_{2}{\mathrm{O}}_{4}$, $\mathrm{Zn}{\mathrm{Al}}_{2}{\mathrm{O}}_{4}$, $\mathrm{Zn}{\mathrm{Ga}}_{2}{\mathrm{O}}_{4}$, and $\mathrm{Zn}{\mathrm{In}}_{2}{\mathrm{O}}_{4}$ are normal spinels with a cubic lattice. Order-disorder transition behaviors are examined using Monte Carlo simulations. The order-disorder transition to exchange octahedral and tetrahedral cations takes place as commonly accepted. In inverse spinels, a new kind of transition to exchange II and III cations in octahedral sites can be recognized, which has not been reported experimentally. Their transition temperatures are evaluated.