'Soft' phonon modes, structured diffuse scattering and the crystal chemistry of Fe-bearing sphalerites
- Research School of Chemistry, Australian National University, Canberra, ACT, 0200 (Australia)
- Mineralogy Department, South Australian Museum, Adelaide, South Australia (Australia)
Electron diffraction has been used to carefully investigate the reciprocal lattices of a range of iron-bearing sphalerites looking for evidence of Fe clustering and/or Fe/Zn ordering in the form of either additional satellite reflections or a structured diffuse intensity distribution accompanying the strong Bragg reflections of the underlying sphalerite-type average structure. While a highly structured diffuse intensity distribution in the form of transverse polarized {l_brace}110{r_brace}* sheets of diffuse intensity has been detected and found to be characteristic of all compositions, it does not appear to arise from Fe clustering and/or Fe/Zn ordering. Rather inherently low frequency, and therefore strongly thermally excited, phonon modes propagating along reciprocal space directions perpendicular to each of the six <110> real space directions of the average structure are suggested to be responsible for these {l_brace}110{r_brace}* sheets of diffuse intensity. Monte Carlo simulation (for a range of Zn-S, Zn-Zn and S-S interaction strengths) and subsequent Fourier transformation is used to confirm the existence of these low-frequency phonon modes of distortion as well as to show that they are an intrinsic, predictable property of the corner-connected tetrahedral structure of sphalerite. The low-frequency phonon modes involve coupled (Zn, Fe) and S motion in one-dimensional strings along <110> real space directions.
- OSTI ID:
- 20725820
- Journal Information:
- Journal of Solid State Chemistry, Vol. 178, Issue 3; Other Information: DOI: 10.1016/j.jssc.2004.12.011; PII: S0022-4596(04)00653-X; Copyright (c) 2004 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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