Stability of intermetallic compounds: Geometrical and topological aspects

Abstract

We have applied a universal geometrical-topological approach to analyze 23507 robust crystal structures of intermetallic compounds, which are deposited in the Inorganic Crystal Structure Database. All the structures were represented as three-periodic nets and arranged into 2551 topological types each of which possesses a unique system of interatomic bonds. For all 104309 topologically different atoms in these structures their environments (local atomic configurations, LACs) were explored within the first and second coordination shells. In total, 5251 topologically distinct types of coordination polyhedra and 21450 types of two-shell LACs were distinguished and deposited into our interactive database system TopCryst. We have found that the local density of the nearest environment of an atom naturally depends on its coordination number (CN) with a maximum at CN = 9. It was shown that LACs at CN ≥ 9 follow the close packing model of hard balls with Slater's atomic radii. At lower CNs, covalent interactions make a significant contribution that results in a decrease of the local density. Resting upon the dependence between the local density and CN we have proposed criteria for the estimation of the geometric instability (disbalance) of both a separate LAC and the whole intermetallic structure. We have revealed that strong geometric disbalance can be caused by errors in the structural data, incorrect description of the crystal structure, non-metallic nature of the chemical bonding or metastability of the crystalline phase. Thus the instability criteria can serve as important indicators of the structure inconsistency that is especially useful for checking crystallographic information on intermetallics or validating the structural models predicted by theoretical methods.