Vibrational, generally waves

The bending (or deformation) vibrations generally require less energy and take place at longer-wave-length than the corresponding stretching vibrations. 

For optically uniaxial crystals we know that the refractive index values for extraordinary waves are variable, with that for ordinary waves fixed. We can link this observation with that concerning the vibration directions for the two waves travelling along a general wave normal direction the ordinary vibration direction is always perpendicular to the optic axis, while the extraordinary vibration is always in the plane containing the optic axis and wave normal direction. This suggests that we may connect the variation of the refractive index in the crystal with the vibration direction of the light. This concept allows a convenient representation of anisotropic optical properties in the form of a spatial plot of the variation of refractive index as a function of vibration direction. Such a surface is known as the optical indicatrix. 

Thus, from Eqs. 12 and 13, the phonon frequency can be evaluated from the curvature of the calculated energy vs. displacement curve for small displacements. These results can be extended to the case of compounds and to general wave vectors where the lack of symmetry requires the calculation and dlagonalization of the dynamical matrix to obtain the phonon frequencies and polarization vectors. Moreover, this approach allows a detailed investigation of the role of core-core, electron-core, electron kinetic, and electron-electron energies to determine the vibrational frequencies of the solids examined. This kind of information has been valuable in analyzing and understanding phonon anomalies in semiconductors and transition metals. 

Figure 1.20 Atomic vibrations in Wz ZnO. The larger atom represents Zn while the smaller one represents O. X— (1 00), (0 1 0), Z— (0 0 ) represent the optical polarization directions (a) for general wave vector and (b) for zone center phonons.

Of course quantum mechanically the ground vibrational state wave-function is not peaked at the classical turning points but has only one maximum. It is interesting to note that in quantum calculations only one peak was observed at the small-r , the so-called outer", turning point of the collinear system. This effect is quite general and seen in all the systems studied. 

Figure Bl.25.12. Excitation mechanisms in electron energy loss spectroscopy for a simple adsorbate system Dipole scattering excites only the vibration perpendicular to the surface (v ) in which a dipole moment nonnal to the surface changes the electron wave is reflected by the surface into the specular direction. Impact scattering excites also the bending mode v- in which the atom moves parallel to the surface electrons are scattered over a wide range of angles. The EELS spectra show the higlily intense elastic peak and the relatively weak loss peaks. Off-specular loss peaks are in general one to two orders of magnitude weaker than specular loss peaks.

In general, at least three anchors are required as the basis for the loop, since the motion around a point requires two independent coordinates. However, symmetry sometimes requires a greater number of anchors. A well-known case is the Jahn-Teller degeneracy of perfect pentagons, heptagons, and so on, which will be covered in Section V. Another special case arises when the electronic wave function of one of the anchors is an out-of-phase combination of two spin-paired structures. One of the vibrational modes of the stable molecule in this anchor serves as the out-of-phase coordinate, and the loop is constructed of only two anchors (see Fig. 12). 

The ti eatment of the Jahn-Teller effect for more complicated cases is similar. The general conclusion is that the appearance of a linear term in the off-diagonal matrix elements H+- and H-+ leads always to an instability at the most symmetric configuration due to the fact that integrals of the type do not vanish there when the product < / > / has the same species as a nontotally symmetiic vibration (see Appendix E). If T is the species of the degenerate electronic wave functions, the species of will be that of T, ... 

Iditional importance is that the vibrational modes are dependent upon the reciprocal e vector k. As with calculations of the electronic structure of periodic lattices these cal-ions are usually performed by selecting a suitable set of points from within the Brillouin. For periodic solids it is necessary to take this periodicity into account the effect on the id-derivative matrix is that each element x] needs to be multiplied by the phase factor k-r y). A phonon dispersion curve indicates how the phonon frequencies vary over tlie luin zone, an example being shown in Figure 5.37. The phonon density of states is ariation in the number of frequencies as a function of frequency. A purely transverse ition is one where the displacement of the atoms is perpendicular to the direction of on of the wave in a pmely longitudinal vibration tlie atomic displacements are in the ition of the wave motion. Such motions can be observed in simple systems (e.g. those contain just one or two atoms per unit cell) but for general three-dimensional lattices of the vibrations are a mixture of transverse and longitudinal motions, the exceptions... 

In general, increasing the temperature within the stability range of a single crystal structure modification leads to a smooth change in all three parameters of vibration spectra frequency, half-width and intensity. The dependency of the frequency (wave number) on the temperature is usually related to variations in bond lengths and force constants [370] the half-width of the band represents parameters of the particles Brownian motion [371] and the intensity of the bands is related to characteristics of the chemical bonds [372]. 

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