摘要
本文研究了HgI_2-Ag_2S-As_2S_3,HgS-Ag_2S-As_2S_3,PbCl_2-Ag_2S—As_2S_3以及AgCl-Ag_2S-As_2S_3系统的玻璃形成范围。对这些系统玻璃用远红外光谱(100~500cm^(-1))和拉曼光谱进行了研究。计算与分析结果表明,在玻璃结构中有[As_3S_6]环状结构单元,[AsI_(3-x)S_x](x=0,1,2)三角锥体,[HgI_(4-x)S_x](x=0,1,2)四面体以及[AgS_6],[HgS_6]等八面体存在。卤化物中金属原子的空轨道与硫化物中硫原子的孤对电子形成了配位键,卤化物配位多面体与硫化物配位多面体正是通过这种配位键来相互连接的,这种连接构成了硫系—卤化物玻璃的连续无序网络。
The formation regions of glass of HgI_2-Ag_2S-As_2S_3, HgS-Ag_2S-As_2S_3, PbCl_2- Ag_2S-As_2S_3 and AgCl-Ag_2S-As_2S_3 systems have been obtained. The structures of these glasses have been investigated by means of far-infrared transmission spectra and Raman spectra. The ring groups of [As_3S_6] are formed by the addition of Ag_2S into As_2S_3 glass. The structural units of [AsI_(3-x)S_x](x=0,l,2) pyramids and [HgI_(4-x)S_x](x=0,l,2) tetrahedra are formed by the addition of HgI_2 into As_2S_3. The [AsS_3] pyramids is interconnected with the [HgI_4] tetrahedra through the coordinate bonds formed by the empty orbitals of Hg atoms in HgI_2 and the lone-pair electrons of S atoms in As_2S_3. This connection composes the network of HgI_2-As_2S_3 glasses. The structure of HgS-Ag_2S-As_2S_3 glasses is composed of[AsS_3] pyramids, [As_3S_6] rings, [AgS_6] and [HgS_6] octahedra. The [AsS_3] is interconnected with through the sulfur bridges or sharing their edges of these polyhedra.
基金
高等学校博士学科点专项科研基金
关键词
硫系玻璃
卤化物
形成
振动光谱
chalcogenids glass
chalco-halide glass
glass formation
vibrational spectra