Alkali halides ionic insulators

However, in the last two decades it has been shown experimentally [1,7, 8,12-14] and theoretically [15-18] that in many wide-gap insulators including alkali halides the primary mechanism of the Frenkel defect formation is subthreshold, i.e., lattice defects arise from the non-radiative decay of excitons whose formation energy is less than the forbidden gap of solids, typically 10 eV. These excitons are created easily by X-rays and UV light. Under ionic or electron beam irradiations the main portion of the incident particle... 

B. Atom-Multiphonon Scattering Time-of-Flight Scattering Instrument Clean Crystalline Surfaces Ionic Insulators A. Alkali Halides... 

The alkali halides are the prototypical ionic insulator materials. The ions all have closed shell configurations with essentially localized electronic dis-... 

Radiation-induced decomposition of insulating solids has been the subject of extensive research for many years. Because of their structural simplicity, the alkali and silver halides have perhaps received the widest attention. Studies of radiation-induced decomposition in azides could represent the next logical step in structural complexity. The azides in many respects are similar to the halides. Like the alkali halides, the alkali azides are primarily ionically bonded with band gaps of the order of 8 eV. Like the halides, there are azides with smaller band gaps (less than 4 eV). Important differences between the halides and azides are the presence of the triatomic azide anion and the lattice symmetry differences, which are perhaps a result of the nonspherical charge distribution on the azide ion. The salient questions which arise for the purpose of this chapter when one compares the azides to the hahdes are How does the the presence of the molecular anion influence radiation-induced decomposition are new and/or different kinds of defects produced how does the azide molecular anion influence the defect production process ... 

Diffusion in ionic materials occurs primarily by the movement of charged species. Therefore, the application of an electric field can provide a very powerful driving force for mass transport. There have been numerous studies on the effects of electric fields on transport phenomena. Several studies have been performed on the evaporation of alkali halides in the presence of an external field. These investigations showed that the application of an electric field enhanced the evaporation of the crystal species. Similar studies have been performed on oxide ionic conductors, including ZrOi and p-aluminas. However, only a few experiments have been performed on classical insulating oxides such as a-A Os and MgO (perhaps because they are insulators). 

In Section 2.3 the structural and optical properties of neutral and cationic Na clusters at r = 0 K as functions of size are presented and compared with experimental data recorded at low temperature. The temperature-dependent line-broadening will be illustrated by the example of Na9, since in this case a comparison with experimental data at different temperatures is particularly instructive. In Section 2.4 the results of ab initio molecular dynamics (AIMD) studies on Li9 will serve to show different temperature behavior of distinct types of structures as well as their isomerization mechanisms. The study of possible metal-insulator transitions and segregation into metallic and ionic parts in finite systems carried out on prototypes of nonstoichiometric alkali halide and alkali hydride clusters with single and multiple excess electrons is presented in Section 2.5. A comparison of structural and optical characteristics of Na F and lAnUm (n > m) series allows us to illustrate the influence of different bonding properties. 

The ground-state properties of nonstoichiometrie X Y clusters (X = Na, Li, K and Y = Cl, F) with single and multiple excess electrons have been extensively studied experimentally [41-43] and theoretically [44-46] since they are good candidates for possible metal-insulator transitions and metallic-ionic segregation in finite systems. Hydrogenation of lithium clusters has been also investigated [47, 48]. It is of interest to establish similarities and differences among properties of alkali halide and alkali hydride clusters, since both bulk materials have a common structure but the electron affinities of F and H atoms are very different (3.4 versus 0.75 eV). The question can be raised to what extent these differences are reflected in properties of small finite systems. 

Insulators in which atoms have completely filled electronic shells, such as the noble elements or the purely ionic alkali halides (composed of atoms from columns I and VII of the Periodic Table) are actually the simplest cases the atoms or ions in these solids differ very little from isolated atoms or ions, because of the stability of the closed electronic shells. The presence of the crystal produces a very minor perturbation to the atomic configuration of electronic shells. The magnetic behavior of noble element solids and alkali halides predicted by the analysis at the individual atom or ion level is in excellent agreement with experimental measurements. 

Ionic Cations and anions Electrostatic, non-directional Hard, brittle, crystals of high m.t. moderate insulators melts are conducting Alkali metal halides... 

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