Pseudoatoms and preferred skeletons in crystals

Abstract

The generalization of the Zintl-Klemm concept provides a universal formulation of a crystal structure in terms of universal building skeletons formed by Klemms pseudoatoms: atoms that behave structurally according to their formal total electron charge. An important difference in this novel view is that charge is considered to be transferred, in the strict Zintls sense, from the donor cations to the building skeleton as a whole, not specifically to a given atom or ion. Although application is restricted to (IV)-(IV) compounds (group 14 structures), the principle seems to be universal and can be applied to understand, to relate and to predict the structure of complex compounds on the basis of more simple structures, e.g. a given AB skeleton provides the building block for A 2 B, AB 2, ABX m etc. compounds of a very different nature. The application of such a principle only requires information on the constituent atoms and on the existing phases of the p-block elements (observed under ambient and high-pressure and/or high-temperature conditions). The ideas introduced here demonstrate, for the first time, that a generalization of the Zintl-Klemm concept is possible and that such a generalization helps to establish a univocal link between chemical composition (in terms of pseudoatoms) and the crystalline structures observed experimentally. © International Union of Crystallography 2007.