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Preliminary evaluation of local structure and speciation of lanthanoids in aqueous solution, iron hydroxide, manganese dioxide, and calcite using the L$$_{3}$$-Edge X-ray absorption near edge structure spectra

Ota, Atsuyuki*; Tanaka, Kazuya ; Tsuno, Hiroshi*

We investigated the application of L$$_{3}$$-edge XANES spectra to the local structural analysis of lanthanoids in aqueous solution, iron hydroxide, manganese dioxide, and calcium carbonate. For each lanthanoid, the full width at half maximum (FWHM) values of lanthanoid compounds roughly decreased with increasing coordination numbers. However, they did not strictly reflect the local coordination sphere of the lanthanoid complex, but were rather sensitive to their chemical forms. The relationship between the magnitude of the FWHM values was determined by the crystal field splitting or degeneracy of 5d orbitals. The systematic variation of FWHM can be explained by the ligand strength of the ligand molecules (-H$$_{2}$$O$$^{0}$$, -O$$^{-}$$, -OH$$^{-}$$, -CO$$_{3}$$$$^{2-}$$, -Cl$$^{-}$$, and -O$$^{2-}$$) that cause the crystal field splitting. Therefore, the FWHM values of L$$_{3}$$-edge XANES of lanthanoid compounds may be more useful in speciation analysis rather than structural analysis such as EXAFS.

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Category:Chemistry, Physical

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