论文标题

TB2O3在压缩下的结构和晶状体 - 动力学特性:一项与稀土和相关倍烷氧化物的比较研究

Structural and lattice-dynamical properties of Tb2O3 under compression: a comparative study with rare-earth and related sesquioxides

论文作者

Ibáñez, Jordi, Sans, Juan Ángel, Cuenca-Gotor, Vanesa, Oliva, Robert, Gomis, Óscar, Rodríguez-Hernández, Plácida, Muñoz, Alfonso, Rodríguez-Mendoza, Ulises, Velázquez, Matías, Veber, Philippe, Popescu, Catalin, Manjón, Francisco Javier

论文摘要

我们报告了曲二氧化物(TB2O3)的高压结构和振动特性的联合实验和理论研究。粉末X射线衍射和拉曼散射测量结果表明,立方(C-Type)TB2O3经历了两种相变高达25 GPA。我们观察到在〜7 GPa处向单斜晶(B型)相向单斜晶(B型)相的第一个不可逆的重建性过渡,然后在〜12 GPA时从单斜层到三角骨(A-type)阶段进行了可逆的位移过渡。因此,发现TB2O3遵循在其他与TB大原子质量的阳离子的其他立方稀有地二氧化物中发现的众所周知的C-B-A相变。我们的从头算理论计算预测了三个阶段的相变压力和大量模量,这与实验结果相当一致。此外,已经监测了这三个阶段的拉曼活性模式,这是压力和晶格 - 动力学计算的函数,使我们能够在C型相中确认实验性声子模式的分配,并在B-和A-A-A-type相中的大多数振动模式的对称性分配。最后,我们提取散装模量和拉曼活性模式频率及其在TB2O3的三个阶段的压力系数。这些结果与报道的稀土和其他相关倍氧化物的结果进行了彻底比较和讨论。结论是,这些技术相关化合物的所有三个阶段的体积和大量模量的演变与阳离子离子半径的第三强度相对于几乎线性的趋势。

We report a joint experimental and theoretical investigation of the high-pressure structural and vibrational properties of terbium sesquioxide (Tb2O3). Powder x-ray diffraction and Raman scattering measurements show that cubic (C-type) Tb2O3 undergoes two phase transitions up to 25 GPa. We observe a first irreversible reconstructive transition to the monoclinic (B-type) phase at ~7 GPa and a subsequent reversible displacive transition from the monoclinic to the trigonal (A-type) phase at ~12 GPa. Thus, Tb2O3 is found to follow the well-known C-B-A phase transition found in other cubic rare-earth sesquioxides with cations of larger atomic mass than Tb. Our ab initio theoretical calculations predict phase transition pressures and bulk moduli for the three phases in rather good agreement with experimental results. Moreover, Raman-active modes of the three phases have been monitored as a function of pressure and lattice-dynamics calculations have allowed us to confirm the assignment of the experimental phonon modes in the C-type phase as well as to make a tentative assignment of the symmetry of most vibrational modes in the B- and A-type phases. Finally, we extract the bulk moduli and the Raman-active modes frequencies together with their pressure coefficients for the three phases of Tb2O3. These results are thoroughly compared and discussed in relation to those reported for rare-earth and other related sesquioxides. It is concluded that the evolution of the volume and bulk modulus of all the three phases of these technologically relevant compounds exhibit a nearly linear trend with respect to the third power of the ionic radii of the cations.

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