Quantitative Advances in the Zintl–Klemm Formalism

Revisiting the Zintl–Klemm Concept: A2AuBi (A = Li or Na)

“…We did not consider spinorbit coupling, which may well have an effect as revealed in our previous study on thallides. [25] We believe that such relativistic effects are not the determining factors here because the "ribbon"/"diamond" structural contrast also exists between Na 2 AgSb [26] and NaIn, [27] where relativistic effects are much less significant. For structural optimization, the conjugate gradient algorithm [28] was applied.…”

The Crystal Orbital Hamilton Population (COHP) Method as a Tool to Visualize and Analyze Chemical Bonding in Intermetallic Compounds

“…For instance, Wade´s rules [77,78] or the Zintl concept [5][6][7][8][9][10] are prominent electron-counting schemes being typically applied to recognize the valence bonds in solid-state materials with polyanionic clusters and monoatomic counterions. More recent research on the components of the active-metal (main-groups I, II, and the scandium-group elements)−gold−post-transition-metal systems identified several materials composed of polyanionic clusters possessing fewer valence electrons relative to those in Zintl phases [15].…”

“…For the case of solid-state materials, in particular ionic salts, first explorations to establish relationships between the structural arrangements and the electron counts of such solids employed empirical data and resulted in various solid-state rules which, for instance, were based on the ratios of ionic radii, the "strengths" of the electrostatic bonds, and the connectivities between diverse coordination polyhedra [4]. Further research on the distributions of the valence electrons in intermetallic compounds revealed additional notions, e.g., those first proposed by Zintl [5][6][7][8][9][10] and Hume-Rothery [11][12][13], respectively, to somehow correlate structural arrangements and the atoms' electronic nature. Even today, however, the existence of intermetallic compounds for which the electronic structures and, furthermore, the nature of bonding cannot be trivially categorized by applying one of the aforementioned concepts [14,15] underlines the need for different means in order to reveal the bonding nature in such materials.…”

Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures

“…Heavier analogs of such clusters with As and Sb are also known [16][17][18]. Similar to other intermetallics, the electronic structures of polyphosphides can be rationalized by application of the Zintl concept [19,20]. Zintl theory implies the valence electrons of electropositive atoms are donated to more electronegative atoms.…”

“…The crystal structure of Ba 2 P 7 X can be described as consisting of two distinct ionic layers, [ (Figure 2a). According to the Zintl concept [19,20], the Ba 2 P 7 X compounds are electron balanced. The barium and halogen atoms realize their electron octet by donating and accepting two and one electrons, respectively.…”