Framework bands

Figure 2. Far-ir spectra of Na-A, recorded at room temperature (A) Hydrated (B) After a 400°C in situ vacuum dehydration. F denotes a framework band.

Both the Bronsted acid sites (H-X), generated via proton attack of the framework (bands around 3650 and 3580 cm ) and the SH groups (band around 2560 cm ) were detected by IR. As could be shown via quantitative evaluation of these bands, their intensities - and this means the density of the OH and SH groups - were correlated to the population of the Sill sites of the faujasite structure by Na+ cations ([454,455] see Fig. 23). 

Electronic spectra are almost always treated within the framework of the Bom-Oppenlieimer approxunation [8] which states that the total wavefiinction of a molecule can be expressed as a product of electronic, vibrational, and rotational wavefiinctions (plus, of course, the translation of the centre of mass which can always be treated separately from the internal coordinates). The physical reason for the separation is that the nuclei are much heavier than the electrons and move much more slowly, so the electron cloud nonnally follows the instantaneous position of the nuclei quite well. The integral of equation (BE 1.1) is over all internal coordinates, both electronic and nuclear. Integration over the rotational wavefiinctions gives rotational selection rules which detemiine the fine structure and band shapes of electronic transitions in gaseous molecules. Rotational selection rules will be discussed below. For molecules in condensed phases the rotational motion is suppressed and replaced by oscillatory and diflfiisional motions. 

The diffusion, location and interactions of guests in zeolite frameworks has been studied by in-situ Raman spectroscopy and Raman microscopy. For example, the location and orientation of crown ethers used as templates in the synthesis of faujasite polymorphs has been studied in the framework they helped to form [4.297]. Polarized Raman spectra of p-nitroaniline molecules adsorbed in the channels of AIPO4-5 molecular sieves revealed their physical state and orientation - molecules within the channels formed either a phase of head-to-tail chains similar to that in the solid crystalline substance, with a characteristic 0J3 band at 1282 cm , or a second phase, which is characterized by a similarly strong band around 1295 cm . This second phase consisted of weakly interacting molecules in a pseudo-quinonoid state similar to that of molten p-nitroaniline [4.298]. 

The optimised interlayer distance of a concentric bilayered CNT by density-functional theory treatment was calculated to be 3.39 A [23] compared with the experimental value of 3.4 A [24]. Modification of the electronic structure (especially metallic state) due to the inner tube has been examined for two kinds of models of concentric bilayered CNT, (5, 5)-(10, 10) and (9, 0)-(18, 0), in the framework of the Huckel-type treatment [25]. The stacked layer patterns considered are illustrated in Fig. 8. It has been predicted that metallic property would not change within this stacking mode due to symmetry reason, which is almost similar to the case in the interlayer interaction of two graphene sheets [26]. Moreover, in the three-dimensional graphite, the interlayer distance of which is 3.35 A [27], there is only a slight overlapping (0.03-0.04 eV) of the HO and the LU bands at the Fermi level of a sheet of graphite plane [28,29],... 

The structure of CaB contains bonding bands typical of the boron sublattice and capable of accommodating 20 electrons per CaB formula, and separated from antibonding bands by a relatively narrow gap (from 1.5 to 4.4 eV) . The B atoms of the B(, octahedron yield only 18 electrons thus a transfer of two electrons from the metal to the boron sublattice is necessary to stabilize the crystalline framework. The semiconducting properties of M B phases (M = Ca, Sr ", Ba, Eu, Yb ) and the metallic ones of M B or M B5 phases (Y, La, Ce, Pr, Nd ", Gd , Tb , Dy and Th ) are directly explained by this model . The validity of these models may be questionable because of the existence and stability of Na,Ba, Bft solid solutions and of KB, since they prove that the CaB -type structure is still stable when the electron contribution of the inserted atom is less than two . A detailed description of physical properties of hexaborides involves not only the bonding and antibonding B bands, but also bonds originating in the atomic orbitals of the inserted metal . ... 

Assuming perfect stoichiometric structures, the stabilization of the boron frameworks of MB2, MB4, MBg, MBj2 and elemental B requires the addition of two electrons from each metal atom. Whatever the Bj2 unit, icosahedron or cubooctahe-dron, 26 electrons are required for internal bonding and 12 for external bonding. Since the 12 B possesses only 36 electrons, the metal must supply two electrons to each Bi2 group. The results for YB,2 are consistent with this model measurements indicate that one electron per Y is delocalized in the conduction band. ... 

The IR spectra of silicon oxides, in the framework region mode, is dominated by a strong absorption around 1000 cm due the anti-symmetric stretching of the Si - 0 - Si unit (Raman inactive mode) and by a less intense absorption around 800cm due the symmetric stretching of the Si-O-Si unit (Raman active mode). In the transparency window between these two modes, the IR spectra of TS-1 shows an additional absorption band located at 960 cm ... 

Fig. 2e), virtually absent in perfect siUcalite-1 and immediately identified as a fingerprint of TS-1 material [37,52-55,63,70,71]. A qualitative correlation between the intensity of the infrared band at 960 cm and Ti content has been observed since the first synthesis of TS-1. Indeed, the occurrence of that band is one of the distinctive features of the material cited in the original patent [7]. However, the quantitative correlation has been reported only very recently by Ricchiardi et al. [52], owing to very serious experimental problems related to the saturation of the IR framework modes, hi the same work, the nature of the 960 cm band has been discussed in terms of theoretical calculations based on both cluster and periodical approaches. 

In the early 1990s Raman spectroscopy was applied to the characterization of TS-1 catalysts [55,56]. In such experiments, beside the 960 cm band, already observed by IR spectroscopy (see Sect. 3.5), a new component at 1125 cm was detected by Scarano et al. [55] (see Fig. 2f). The 1125 cm band was recognized to be a fingerprint of the insertion of Ti atoms in the ze-olitic framework [55]. This band could not be observed in the IR studies as totally overshadowed by an extremely intense band around 1000 cm due to Si02 framework modes (Fig. 2e). 

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. 

Similar observations have been made on a few silaaromatics, such as silabenzene and 1-silatoluene, but it is not known which of the many absorption bands observed are associated with the silicon-carbon framework. The same is true for the stable silenes such as (Me3Si)2Si=C(OSi Me3)Ad. Both in solution and the solid state, a number of bands were observed in the region 1300-930 cm-1, but it is not known with certainty which are associated with the Si=C bond. 

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