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The puzzling structure of Cu 5 FeS 4 (bornite) at low temperature.

The crystal structure of Cu5 FeS4 (bornite) has been investigated using synchrotron X-ray powder diffraction at temperatures between 10 and 275 K. Diffraction data confirm that bornite crystallizes in the orthorhombic space group Pbca at 275 K. The unit-cell volume decreases continuously on cooling, but undergoes an abrupt contraction below ∼65 K, where a first-order Pbca→Pca21 structural transition takes place. The primary active mode yielding the observed ordered structure corresponds to the irreducible representation Γ2 - , with wavevector (0,0,0). Pair distribution function analysis shows strong discrepancies between the local and the average structure. The average Fe-S bond length obtained through the EXAFS local probe is consistent with the values independently provided by X-ray powder diffraction data, strongly supporting the preferred location of Fe.

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