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Ishimaru, Satoko
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article
Single-crystal structure refinements and Debye temperatures of Ir<sub>2</sub>S<sub>3</sub> kashinite and Rh<sub>2</sub>S<sub>3</sub> bowieite
Abstract
<jats:p>Single crystals of Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> (diiridium trisulfide) and Rh<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> (dirhodium trisulfide) were grown in evacuated silica-glass tubes using a chemical transport method and their crystal structures were determined by single-crystal X-ray diffraction analysis. These compounds have a unique sesquisulfide structure in which pairs of face-sharing octahedra are linked into a three-dimensional structure by further edge- and vertex-sharing. Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> and Rh<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> had similar unit-cell parameters and bond distances. The atomic displacement parameter (MSD: mean-square displacement) of each atom in Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> was considerably smaller than that in Rh<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub>. The Debye temperatures (Θ<jats:sub>D</jats:sub>) estimated from the observed MSDs for the Ir, S1 and S2 sites in Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> were 259, 576 and 546 K, respectively, and those for Rh, S1 and S2 in Rh<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> were 337, 533 and 530 K, respectively. The bulk Debye temperature for Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> kashinite (576 K) was found to rank among the higher values reported for many known sulfides. The bulk Debye temperature for Rh<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> bowieite (533 K) was lower than that for Ir<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> kashinite, which crystallizes in the early sequences of mineral crystallization differentiation from the primitive magma in the Earth's mantle.</jats:p>