Ba2HgS5-A Molecular Trisulfide Salt with Dumbbell-like (HgS2)2- Ions
Ba2HgS5-A Molecular Trisulfide Salt with Dumbbell-like (HgS2)2- Ions
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DOI：
10.1021/ic500388s
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发表时间：
2014-05-05
影响因子：
4.6
通讯作者：
Kanatzidis, Mercouri G.
中科院分区：
文献类型：
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作者：
Islam, Saiful M.;Im, Jino;Kanatzidis, Mercouri G.
通过冷却BaS、HgS和元素硫的熔融混合物来合成Ba 2 HgS 5。它在正交晶系Pnma空间群中结晶，a = 12.190（2）埃，B = 8.677（2）埃，c = 8.371（2）埃，d（计算）= 4.77 g cm-3。其晶体结构由孤立的哑铃形（HgS 2）（2-）和V形S-3（2-）离子组成。这些分子阴离子通过Ba 2+阳离子进行电荷平衡。拉曼光谱显示了三个强带，分别来自S-3（2-）离子的对称、非对称和弯曲振动模式。X射线光电子能谱分析证实了三硫化物物种的存在。Ba 2 HgS 5具有类似于2.4eV的带隙。电子能带结构计算表明，带隙基本上由S-3（2-）基团的硫原子的p轨道定义。
Ba2HgS5 was synthesized by cooling a molten mixture of BaS, HgS, and elemental sulfur. It crystallizes in the orthorhombic Pnma space group with a = 12.190(2) angstrom, b = 8.677(2) angstrom, c = 8.371(2) angstrom, and d(calc) = 4.77 g cm-3. Its crystal structure consists of isolated dumbbell-shaped (HgS2)(2-) and v-shaped S-3(2-) ions. These molecular anions are charge-balanced by Ba2+ cations. Raman spectroscopy shows three strong bands originating from symmetric, asymmetric, and bending vibrational modes of the S-3(2-) ions. X-ray photoelectron spectroscopic analysis confirms the presence of the trisulfide species. Ba2HgS5 has a bandgap of similar to 2.4 eV. Electronic band structure calculations show that the bandgap is defined essentially by the p-orbitals of the sulfur atoms of the S-3(2-) group.