Crystallization Debye-process

Dislocation motion in covalent crystals is thermally activated at temperatures above the Einstein (Debye) temperature. The activation energies are well-defined, and the velocities are approximately proportional to the applied stresses (Sumino, 1989). These facts indicate that the rate determining process is localized to atomic dimensions. Dislocation lines do not move concertedly. Instead, sharp kinks form along their lengths, and as these kinks move so do the lines. The kinks are localized at individual chemical bonds that cross the glide plane (Figure 5.8). 

According to the model, a perturbation at one site is transmitted to all the other sites, but the key point is that the propagation occurs via all the other molecules as a collective process as if all the molecules were connected by a network of springs. It can be seen that the model stresses the concept, already discussed above, that chemical processes at high pressure cannot be simply considered mono- or bimolecular processes. The response function X representing the collective excitations of molecules in the lattice may be viewed as an effective mechanical susceptibility of a reaction cavity subjected to the mechanical perturbation produced by a chemical reaction. It can be related to measurable properties such as elastic constants, phonon frequencies, and Debye-Waller factors and therefore can in principle be obtained from the knowledge of the crystal structure of the system of interest. A perturbation of chemical nature introduced at one site in the crystal (product molecules of a reactive process, ionized or excited host molecules, etc.) acts on all the surrounding molecules with a distribution of forces in the reaction cavity that can be described as a chemical pressure. 

Compared with the momentum of impinging atoms or ions, we may safely neglect the momentum transferred by the absorbed photons and thus we can neglect direct knock-on effects in photochemistry. The strong interaction between photons and the electronic system of the crystal leads to an excitation of the electrons by photon absorption as the primary effect. This excitation causes either the formation of a localized exciton or an (e +h ) defect pair. Non-localized electron defects can be described by planar waves which may be scattered, trapped, etc. Their behavior has been explained with the electron theory of solids [A.H. Wilson (1953)]. Electrons which are trapped by their interaction with impurities or which are self-trapped by interaction with phonons may be localized for a long time (in terms of the reciprocal Debye frequency) before they leave their potential minimum in a hopping type of process activated by thermal fluctuations. 

The use of a monochromator produces a change in the relative intensities of the beams diffracted by the specimen. Equation (4-19), for example, was derived for the completely unpolarized incident beam obtained from the x-ray tube. Any beam diffracted by a crystal, however, becomes partially polarized by the diffraction process itself, which means that the beam from a crystal monochromator is partially polarized before it reaches the specimen. Under these circumstances, the usual polarization factor (1 - - cos 26)12, which is included in Eqs. (4-19) through (4-21), must be replaced by the factor (1 + cos 2a cos 20)/(l -I- cos 2a), where 2a is the diffraction angle in the monochromator (Fig. 6-16). Since the denominator in this expression is independent of 6, it may be omitted the combined Lorentz-polarization factor for crystal-monochromated radiation is therefore (1 + cos 2a cos 20)/sin 6 cos 6. This factor may be substituted into Eqs. (4-19) and (4-20), although a monochromator is not often used with a Debye-Scherrer camera, or into Eq. (4-21), when a monochromator is used with a diffractometer (Sec. 7-13). But note that Eq. (4-20) does not apply to the focusing cameras of the next section. 

We only consider the one-phonon-assisted process in the weak-coupling limit, where D and A are taken to be the same species. For an isotropic crystal, the donor-acceptor ET rate is given, for a large energy mismatch (-100 cm1) between the donor and acceptor excitations, AE (also equal to the phonon energy), under the Debye phonon model, by the expression [368]... 

Equation (53) describes Debye relaxation. Magnesium and calcium-doped lithium fluorides have a characteristic Debye relaxation diagram from vhich the dopant concentration and the relaxation time can be deduced. Many others crystals containing mobile lattice defects have similar Debye s relaxation processes. Major understanding of the structure of color centers results from dielectric relaxation spectra. Nuclear magnetic resonance, optical and Raman spectroscopy can be used efficiently in conjunction vith dielectric spectroscopy. 

The recoil-free emission and resonant absorption processes necessary to observe the Mossbauer spectrum can only occur for nuclei bound into a solid. The fraction of such events depends on the 7-ray energy and the vibrational properties of the crystal. Hence, in principle from temperature-dependent measurements of the absorption area, information about crystal dynamics, such as the Debye temperature, can be obtained. 

From our data we deduced the Debye temperature of 135 K for the crystal, in good agreement with the value of 148 K found by Nusawa et al. (1975). At yet lower temperatures (less than 70 K), the curve indicates coexistence of two opposing effects the Raman process and occurrence of antifeiromagnetic ordering with a Neel temperature close to absolute zero. As a consequence, we could not confirm the influence of phase transition on relaxation mechanisms. 

In the study of dielectric relaxation, temperature is an important variable, and it is observed that relaxation times decrease as the temperature increases. In Debye s model for the rotational diffusion of dipoles, the temperature dependence of the relaxation is determined by the diffusion constant or microscopic viscosity. For liquid crystals the nematic ordering potential contributes to rotational relaxation, and the temperature dependence of the order parameter influences the retardation factors. If rotational diffusion is an activated process, then it is appropriate to use an Arrhenius equation for the relaxation times ... 

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