Abstract

Crystallochemical analysis with the use of Voronoi–Dirichlet polyhedra (VDPs) has been performed for 711 sulfides, whose structures contain 1199 coordination polyhedra LnS_n, where Ln is a lanthanide from La to Lu. It has been established that the sulfides incorporate Ln(II), Ln(III), and Ce(IV) atoms bonding from 6 to 10 sulfur atoms, which exist in the form of S^2– or S^– ions. The VDP parameters provide the possibility to determine the valence state of Ln atoms in the structures of sulfides and distinguish S^2– or S^– ions. The VDPs of 2913 sulfur atoms have been characterized to establish the dependence between the multiplicity of S–S bonds and their length. A quantitative estimate of lanthanide contraction in Ln^IIIX_n polyhedra is given depending on the nature of chalcogen Х (O, S, Se, or Te).

中文翻译：

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硫化物中镧系元素立体化学的特殊特征

摘要

使用Voronoi-Dirichlet多面体（VDPs）对711个硫化物进行了晶体化学分析，其结构包含1199个配位多面体LnS _n，其中Ln是从La到Lu的镧系元素。现已确定，硫化物结合了Ln（II），Ln（III）和Ce（IV）原子，它们键结有6至10个硫原子，它们以S ^2–或S ^–离子的形式存在。VDP参数可以确定硫化物结构中Ln原子的价态并区分S ^{2 –}或S ^–离子。2913个硫原子的VDP被表征为建立S–S键的多样性与其长度之间的依存关系。根据硫族元素Х（O，S，Se或Te）的性质，对Ln ^III X _n多面体中镧系元素的收缩进行了定量估计。