Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.
Inorg Chem. 2012 Jun 18;51(12):6868-75. doi: 10.1021/ic300628m. Epub 2012 Jun 4.
The postspinel mineral MgAl(2)O(4) exists only under the severe pressure conditions in the subducted oceanic lithosphere in the Earth's deep interior. Here we report that its analogous oxide CdRh(2)O(4) exhibits a structural transition to a quenchable postspinel phase under a high pressure of 6 GPa at 1400 °C, which is within the general pressure range of a conventional single-stage multianvil system. In addition, the complex magnetic contributions to the lattice and metal nonstoichiometry that often complicate investigations of other analogues of MgAl(2)O(4) are absent in CdRh(2)O(4). X-ray crystallography revealed that this postspinel phase has an orthorhombic CaFe(2)O(4) structure, thus making it a practical analogue for investigations into the geophysical role of postspinel MgAl(2)O(4). Replacement of Mg(2+) with Cd(2+) appears to be effective in lowering the pressure required for transition, as was suggested for CdGeO(3). In addition, Rh(3+) could also contribute to this reduction, as many analogous Rh oxides of aluminous and silicic minerals have been quenched from lower-pressure conditions.
尖晶石后矿物 MgAl(2)O(4) 仅存在于地球深部俯冲大洋岩石圈的极端高压条件下。在这里,我们报告称,其类似的氧化物 CdRh(2)O(4) 在 1400°C 时的 6 GPa 高压下表现出可淬火尖晶石后相的结构转变,这处于常规单级多砧系统的一般压力范围内。此外,晶格和金属非化学计量的复杂磁性贡献,这些通常会使对 MgAl(2)O(4) 的其他类似物的研究变得复杂,在 CdRh(2)O(4) 中不存在。X 射线晶体学表明,这种尖晶石后相具有正交 CaFe(2)O(4)结构,因此使其成为研究尖晶石后 MgAl(2)O(4)地球物理作用的实际类似物。用 Cd(2+) 替代 Mg(2+) 似乎可以有效地降低转变所需的压力,正如 CdGeO(3) 所建议的那样。此外,由于许多类似的含铝和含硅矿物的 Rh 氧化物已经从较低的压力条件下淬火,因此 Rh(3+) 也可能有助于降低压力。