Yoshiasa Akira, Kitahara Ginga, Tokuda Makoto, Ishimaru Satoko, Ono Shin Ichiro, Terai Kunihisa, Nakatsuka Akihiko, Sugiyama Kazumasa
Faculty of Advanced Science and Technology, Kumamoto University, Kumamoto, Kumamoto 860-8555, Japan.
Graduate School of Science and Technology, Kumamoto University, Kumamoto, Kumamoto 860-8555, Japan.
Acta Crystallogr C Struct Chem. 2022 Nov 1;78(Pt 11):606-611. doi: 10.1107/S2053229622009603. Epub 2022 Oct 6.
Single crystals of IrS (diiridium trisulfide) and RhS (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. IrS and RhS had similar unit-cell parameters and bond distances. The atomic displacement parameter (MSD: mean-square displacement) of each atom in IrS was considerably smaller than that in RhS. The Debye temperatures (Θ) estimated from the observed MSDs for the Ir, S1 and S2 sites in IrS were 259, 576 and 546 K, respectively, and those for Rh, S1 and S2 in RhS were 337, 533 and 530 K, respectively. The bulk Debye temperature for IrS kashinite (576 K) was found to rank among the higher values reported for many known sulfides. The bulk Debye temperature for RhS bowieite (533 K) was lower than that for IrS kashinite, which crystallizes in the early sequences of mineral crystallization differentiation from the primitive magma in the Earth's mantle.
采用化学传输法在抽真空的石英玻璃管中生长出了IrS（三硫化二铱）和RhS（三硫化二铑）的单晶，并通过单晶X射线衍射分析确定了它们的晶体结构。这些化合物具有独特的倍半硫化物结构，其中成对的共面八面体通过进一步的共边和共顶点连接形成三维结构。IrS和RhS具有相似的晶胞参数和键长。IrS中每个原子的原子位移参数（MSD：均方位移）明显小于RhS中的。根据IrS中Ir、S1和S2位点的观测MSD估计的德拜温度（Θ）分别为259、576和546 K，RhS中Rh、S1和S2的德拜温度分别为337、533和530 K。发现IrS硫铱矿的体德拜温度（576 K）在许多已知硫化物报道的较高值之列。RhS鲍伊矿的体德拜温度（533 K）低于IrS硫铱矿，IrS硫铱矿是在地幔原始岩浆矿物结晶分异的早期序列中结晶的。
