Cation Ordering and Electron Transfer by C Gleitzer; et al

By C Gleitzer; et al

Content material: Mixed-valence iron oxides / C. Gleitzer, J.B. Goodenough -- an alternate method of non-molecular crystal buildings with emphasis at the preparations of cations / M. O'Keefe, B.G. Hyde -- Redox reactions of sulphur-containing amino-acid residues in proteins and metalloproteins, an XPS research / U. Weser -- writer index, volumes 1-61

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As in the system Fe3_xO4, the washing out of the semiconductor-semiconductor transition at Tv, but the retention of strong electron-phonon coupling to above room temperature, shows that the long-range order below Tv in magnetite is only a freezing in of a dynamic coupling established at much higher temperatures; this coupling is presumably, driven by electrostatic Coulomb interactions between the mobile electrons. Such couplings are not associated with itinerant 3 d electrons in metallic oxides.

441/~) end member Zn[Fe2]O4 was seen to be n-type with mobile electrons moving at the bottom of a narrow Fe3+;2+: 3d 6 band, Transport properties intermediate between those expected for small polarons or for itinerant electrons suggest a diffusional motion, but with a motional enthalpy AHm < kT. 411/~) end member Ge[Fe2]O4, the transport and optical properties of high-purity, p-type single crystals - grown by chemical-vapor (TeC14) deposition - indicate that the mobile holes are thermally excited from acceptor sites into a narrow, filled Fe3+/2+: 3 d 6 Mixed-Valence Iron Oxides 47 valence band of itinerant-electron states 215).

However, it is now known that lithium can be inserted either chemically or electrochemically at room temperature into mangano- and ferrospinels without perturbing the [B2]X4 framework 192). The lithium enter the interstitial 16 c sites as Li + ions and donate an electron to the host matrix, reducing Fe 3+ to Fe 2t or Mn 3t to Mn 2t or Mn 4t to Mn 3t, for example. The electrostatic force between the Li + ions and the host A-site cation appears to displace the A-site cation to positions 16 c, so the product has cations only on octahedral sites of a close-packed oxide-ion array; but a peculiar cation ordering persists: the octahedral 16 d sites of the cubic-spinel space group Fd 3 m remain occupied as in the original spinel phase, and the Li ÷ and originally A-site cations are randomly distributed with any vacancies on the 16 c sites.

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