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| Content Provider | Royal Society of Chemistry (RSC) |
|---|---|
| Author | Howe, A. T. Ménil, F. Greenwood, N. N. |
| Copyright Year | 1971 |
| Abstract | The occurrence or absence of cation ordering and the extent of magnetic ordering in complex phases derived from the rutile structure FeF2 have been studied by Mössbauer spectroscopy over a wide range of temperature. The Fe2+ compounds FeCoNiF6, Mg2FeF6, and MgFe2F6 are disordered rutile phases with Néel temperatures corresponding to the weighted average of those of the component metal difluorides. The local variation in nearest-neighbour cation environment leads to a variation in hyperfine magnetic field of ±30 kG about the mean for each compound.The altervalent fluoride LiFe2F6 shows separate spectra from Fe2+ and Fe3+ in both the paramagnetic and the magnetically ordered regions, thus demonstrating the integrity of the individual oxidation states and the absence of electron hopping. The narrow linewidths indicate complete geometric ordering of all cations in the trirutile structure and the repeating cation sequence in the c direction is shown to be Li+(Fe2+↑)(Fe3+↓)Li+(Fe2+↓)(Fe3+↑) leading to overall antiferromagnetic behaviour. By contrast the trirutile compound LiMgFeF6 showed a range of quadrupole splittings consistent with the ordering of Fe3+ into every third layer along the c axis and a randomisation of Li+ and Mg2+ in the intervening two layers; this model was dictated by the absence of magnetic ordering even at 1·4 K, and the spectra at this temperature and at 4·2 K showed instead the effects of slow spin–spin relaxation characteristic of magnetically dilute Fe3+ ions. |
| Starting Page | 2218 |
| Ending Page | 2224 |
| Page Count | 7 |
| File Format | |
| ISSN | 00224944 |
| Volume Number | 0 |
| Journal | Journal of the Chemical Society A: Inorganic, Physical, Theoretical |
| DOI | 10.1039/J19710002218 |
| Language | English |
| Publisher | Royal Society of Chemistry |
| Access Restriction | Open |
| Subject Keyword | Ssbauer Li Ion Rutile Mössbauer spectroscopy Hyperfine structure Magnetic field Fluoride Paramagnetism Antiferromagnetism Quadrupole |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Inorganic Chemistry |
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