Mo~2S~4(i-mnt)~2(Et~4N)~2和(Et~4N)~3K[Mo~2S~4(i-mnt)~2]~2 [i-mnt=S~2C (CN)^2^-]阴离子的能带结构研究

二核钼簇合物Mo~2S~4(i-mnt)~2(Et~4N)~2和(Et~4N)~3KMo~2S~4(i-mnt)~2]~2i-mnt=S~2C(CN)^2^-]的阴离子在晶体中构成独特的链状结构,本文采用扩展的Huckel近似下的紧束缚能带方法,计算了它们的能带结构。结果表明,相邻簇阴离子间存在弱的相互作用,它是形成链状结构的基础。链状结构与晶体的半导体性质相关联。态密度和晶体轨道重叠布居反映了晶体中电荷分布状况及化学成键特点,与晶体结构分析、NMR谱学表征结果相符合。

The investigation on the band structures of the anions of Mo~2S~4(i- mnt)~2(Et~4N)~2 and (Et~4N)~3K[Mo~2S~4(i-mnt)~2]~2 [i-mnt=S~2C(CN)^2^-] complexes

The anions of complexes Mo2S4(i - mnt)2(Et4N)2 and (Et4N)3KMo2S4(i - mnt)2]2i - mnt = S2C(CN)2-] form special chains in the crystals. In this paper, their band structures have been studied by using the tight - binding energy band method within the extended Huckel scheme. It is found that there exist weak interactions between adjacent anions and this kind of interactions is the basis for the formation of the chain. The chain structures are correlated with the semiconducting properties of the crystals. The calculated densities of states and crystal orbital overlap populations show the charge distributions and chemical bonding properties which coincide with the experimental results.