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首页> 外文期刊>Chemistry: A European journal >High-energy X-ray absorption spectroscopy: A new tool for structural investigations of lanthanoids and third-row transition elements
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High-energy X-ray absorption spectroscopy: A new tool for structural investigations of lanthanoids and third-row transition elements

机译：高能X射线吸收光谱法：一种用于研究镧系元素和第三行过渡元素的结构的新工具

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摘要

This is the first systematic study exploring the potential of high-energy EXAFS as a structural tool for lanthanoids and third-row transition elements. The K-edge X-ray absorption spectra of the hydrated lanthanoid(III) ions both in aqueous solution and in solid trifluoromethanesulfonate salts have been studied. The K-edges of lanthanoids cover the energy range from 38 (La) to 65 keV (Lu), while the corresponding energy range for the L,edges is 5.5 (La) to 9.2 keV (Lu). We show that the large widths of the core-hole states do not appreciably reduce the potential structural information in the high-energy K-edge EXAFS data. Moreover, for lanthanoid compounds, more accurate structural parameters are obtained from analysis of K-edge than from L-3-edge EXAFS data. The main reasons are the much wider k range available and the absence of double-electron transitions, especially for the lighter lanthanoids. A comparative K- and L-3-edge EXAFS data analysis of nonahydrated crystalline neodymium(III) trifluoromethanesulfonate demonstrates the clear advantages of K-edge analysis over conventionally performed studies at the L-3-absorption edge for structural investigations of lanthanoid and third-row transition metal compounds. The coordination chemistry of the hydrated lanthanoid(III) ions in aqueous solution and solid trifluoromethanesulfonate salts, based on the results of both the K- and L-3-edge EXAFS data, is thoroughly discussed in the next paper in this series (I. Persson, P. D'Angelo, S. De Panfilis, M. Sandstrom, L. Eriksson, Chem. Eur J. 2008, 14, DOI: 10.1002/chem.200701281).
机译：这是第一个系统研究，探讨了高能EXAFS作为镧系元素和第三行过渡元素的结构性工具的潜力。研究了水溶液中和固体三氟甲磺酸盐中水合镧系元素（III）离子的K边缘X射线吸收光谱。镧系元素的K边覆盖的能量范围为38（La）至65 keV（Lu），而L，edge的对应能量范围为5.5（La）至9.2 keV（Lu）。我们表明，大的芯孔态宽度不会明显降低高能K边EXAFS数据中的潜在结构信息。此外，对于镧系元素化合物，通过分析K-edge比从L-3-edge EXAFS数据可以获得更准确的结构参数。主要原因是可用的k范围宽得多，并且没有双电子跃迁，特别是对于较轻的镧系元素。比较无水结晶三氟甲烷磺酸钕（III）的K和L-3-edge EXAFS数据分析，证明了与传统方法在L-3吸收边缘进行的镧系元素和第三级结构研究相比，K-edge分析具有明显的优势。行过渡金属化合物。基于K和L-3-edge EXAFS数据的结果，水溶液中的水合镧系元素（III）离子和固体三氟甲磺酸盐的配位化学将在本系列的下一篇论文中全面讨论（I. Persson，P.D'Angelo，S.De Panfilis，M.Sandstrom，L.Eriksson，Chem.Eur J.2008，14，DOI：10.1002 / chem.200701281）。

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