High-pressure, high-temperature single-crystal study of Bi-IV.

Bi-IV is the stable high-pressure, high-temperature phase of bismuth at ∼4 GPa and ∼500 K. It was first identified in 1958, but its structure has remained uncertain. An X-ray powder-diffraction study of Bi-IV reported the structure as monoclinic, but a subsequent reinterpretation of the same data concluded that the structure was C-centred orthorhombic (oC16), with the same atomic arrangement as in Cs-V and Si-VI. To resolve the uncertainty over the structure of Bi-IV, we investigated this phase at 3.2 GPa and 465 K by single-crystal synchrotron X-ray diffraction. All of the observed reflections could be indexed on the orthorhombic oC16 structure proposed by Degtyareva, with a=11.191(5) Å, b=6.622(1) Å and c=6.608(1) Å. The spacegroup was confirmed as Cmce. Refinement of the data resulted in an excellent fit (R=2.8% ), and gave atomic coordinates very similar to those of the oC16 structures in Cs-V and Si-VI. [ABSTRACT FROM PUBLISHER]