Zintl phases structures

We shall first review the basic principles of VASP and than describe exemplary applications to alloys and compounds (a) the calculation of the elastic and dynamic properties of a metallic compound (CoSi2), (b) the surface reconstruction of a semiconducting compound (SiC), and (c) the calculation of the structural and electronic properties of K Sbi-j, Zintl-phases in the licpiid state. 

The structural and electronic properties of K-Sb Zintl phases in the crystalline and molten states... 

The chemistry of silicon in very low oxidation states is one of the most fascinating research areas, which can be located between molecular compounds of silicon and elemental (perhaps amorphous) silicon [190-194]. Most interesting results have recently been obtained by structural investigations of siliddes in Zintl phases. However, compounds of silicon with negative oxidation states and very low coordination numbers of 1, 2, and 3 are so far only known in the composite of a crystal lattice. 

Schmidt PC (1987) Electronic Structure of Intermetrallic B 32 Type Zintl Phases. 65 91-133 Schmidt W (1980) Physiological Bluelight Reception. 41 1-44... 

Chemistry, Structure, and Bonding of Zintl Phases and Ions Kauzlarich, S.M.,... 

Schmidt, P. C. Electronic Structure of Intermetallic B 32 Type Zintl Phases. Vol. 65, pp. 91-133. 

As we can see from the last entry in this table, we have deduced only a rule. In InBi there are Bi-Bi contacts and it has metallic properties. Further examples that do not fulfill the rule are LiPb (Pb atoms surrounded only by Li) and K8Ge46. In the latter, all Ge atoms have four covalent bonds they form a wide-meshed framework that encloses the K+ ions (Fig. 16.26, p. 188) the electrons donated by the potassium atoms are not taken over by the germanium, and instead they form a band. In a way, this is a kind of a solid solution, with germanium as solvent for K+ and solvated electrons. K8Ge46 has metallic properties. In the sense of the 8-A rule the metallic electrons can be captured in K8Ga8Ge38, which has the same structure, all the electrons of the potassium are required for the framework, and it is a semiconductor. In spite of the exceptions, the concept has turned out to be very fruitful, especially in the context of understanding the Zintl phases. 

The octet principle, primitive as it may appear, has not only been applied very successfully to the half-metallic Zintl phases, but it is also theoretically well founded (requiring a lot of computational expenditure). Evading the purely metallic state with delocalized electrons in favor of electrons more localized in the anionic partial structure can be understood as the Peierls distortion (cf. Section 10.5). 

When covalent bonds favor neighbors of the same element, the positions c and d can also be occupied by atoms of the same kind as in a or b. This applies to diamond and to the Zintl phase NaTl NaTl can be regarded as a network of Tl particles that form a diamond structure which encloses Na+ ions (cf. Fig. 13.3, p. 134). 

The structure of MnP is a distorted variant of the NiAs type the metal atoms also have close contacts with each other in zigzag lines parallel to the a-b plane, which amounts to a total of four close metal atoms (Fig. 17.5). Simultaneously, the P atoms have moved up to a zigzag line this can be interpreted as a (P-) chain in the same manner as in Zintl phases. In NiP the distortion is different, allowing for the presence of P2 pairs (P ). These distortions are to be taken as Peierls distortions. Calculations of the electronic band structures can be summarized in short 9-10 valence electrons per metal atom favor the NiAs structure, 11-14 the MnP structure, and more than 14 the NiP structure (phosphorus contributes 5 valence electrons per metal atom) this is valid for phosphides. Arsenides and especially antimonides prefer the NiAs structure also for the larger electron counts. 

R. Nesper, Structure and chemical bonding in Zintl phases containing lithium. Progr. Solid State Chem. 20 (1990) 1. 

More often, polyhedral clusters with strong metal-metal (or metalloid-metalloid) bonding are the major structural motifs of classic Zintl phases. These are nominally salts composed of reduced p- (i.e., post-transition) elements that are usually inter-bonded into closed shell polyanions plus active metal cations, originally the alkali... 

Polar intermetallics are loosely referred to as electron-poorer relatives of Zintl phases in which the active metals do not contribute all of their valence electrons, rather they bond with the more electronegative components to some degree. The structures cannot be simply accounted for by octet rules because of substantial delocalized bonding among the atoms. 

Kauzlarich SM (ed) (1996) Chemistry, structure, and bonding of zintl phases and ions. VCH, New York... 

Although numerous Zintl phases have been studied as solids and their structures determined, differences between packing in crystals and solvation in solution frequently cause the clusters to be different in the... 

General characteristics of alloys such as those presented in Fig. 3.3 have been discussed by Fassler and Hoffmann (1999) in a paper dedicated to valence compounds at the border of intermetallics (alkali and alkaline earth metal stannides and plumbides) . Examples showing gradual transition from valence compounds to intermetallic phases and new possibilities for structural mechanisms and bonding for Sn and Pb have been discussed. Structural relationships with Zintl phases (see Chapter 4) containing discrete and linked polyhedra have been considered. See 3.12 for a few remarks on the relationships between liquid and amorphous glassy alloys. 

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