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Presently, we are not able to relate the clusters identified by Mössbauer spectroscopy to any of the structures characterized crystallographically. Therefore, we distinguish the spectroscopically suggested clusters by labels α and β, designating Fe cluster sites with Arabic numerals.
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1- together with three cations in the asymmetric unit. For that material, the oxidized form contributed in zero field and at 4.2 K quadrupole doublets, as expected for a non-Kramers system. Comparison of the Mössbauer spectra of that form with those of the present sample showed that the spectrum of the 2- cluster was nearly the same in both crystals. Matching of the spectra for both samples revealed that the present sample must contain 10-15% of oxidized material, observed as quadrupole doublets. The oxidized fraction is not necessarily the 1- cluster.
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Inversion of the relative intensities of the g = 7.2 and 5.9 resonances with increasing temperature raised the possibility that they belong to different species. Given that the Mössbauer spectra indicate multiple species, the assumption would not be unreasonable.
-
-
-
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69
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2442666039
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-
note
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3)]. Finally, it is not obvious how to relate the Mössbauer components seen in the polycrystalline samples with any of the four structures of cluster 3.
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