School of Chemistry, The University of Sydney, Sydney, NSW 2006 Australia.
Inorg Chem. 2012 Dec 17;51(24):13237-44. doi: 10.1021/ic301677b. Epub 2012 Oct 11.
The zirconates Ln(2)Zr(2)O(7) (Ln = lanthanoid) have been studied using a combination of Zr L-edge X-ray absorption near edge structure (XANES) and synchrotron X-ray and neutron powder diffraction methods. These studies demonstrate that as the size of the lanthanoid cation decreases, the local structure evolves smoothly from the ideal pyrochlore toward the defect fluorite rather than undergoing an abrupt transformation. The Zr L-edge spectrum is found to be extremely sensitive to changes in the local coordination environment and demonstrates an increase in local disorder across the pyrochlore oxides. The sensitivity of the XANES measurements enables us to identify the progressive nature of the transition that could not be detected using bulk diffraction techniques.
镧系元素（Ln）的锆酸盐 Ln2Zr2O7（Ln = 镧系元素）采用 Zr L 边 X 射线吸收近边结构（XANES）和同步加速器 X 射线和中子粉末衍射方法进行了研究。这些研究表明，随着镧系元素阳离子尺寸的减小，局部结构从理想的钙钛矿向缺陷萤石平滑地演变，而不是发生突然的转变。Zr L 边光谱对局部配位环境的变化极为敏感，并证明了整个钙钛矿氧化物的局部无序度增加。XANES 测量的灵敏度使我们能够识别出使用体相衍射技术无法检测到的过渡的渐进性质。
