Crystals dipole structure

Note that the dipole structure in a crystal is stabilized by the applied stress. It becomes unstable when the stress is removed. Thus, the in situ structures of... 

The above properties (a and b) are interpreted by Cohen and Schmidt (21) on the basis of a detailed crystallographic study of photochromic and thermochromic anils. They conclude that photochromic crystals involve structures in which the central portion of adjacent molecules are essentially isolated from one another, so that, to a first approximation the energetics are that of an isolated molecule. On the other hand, when the alignment of the molecular dipoles is such as to give strong intermolecular interactions then the transition to the quinoid form requires much less energy and can occur thermally. For crystals in which thermochromism occurs, the photochemical isomerization is still possible but the reverse reaction is so rapid that no buildup of color is observed. In fact, fluorescence measurements on the thermochromic 5 -chlorosalicylidene-aniline (Fig. 5) indicate that photochemical isomerization precedes the luminescence process via the photochromic route ... 

For example, the 815 cm-l peak shifted to 825 cm i and the doublet at 1730/1750 cm-l, indicative of crystal-like structures has disappeared at the highest shear rate. The spectral changes near 815 cm-1 of Fig. 15a could conceivably correspond to those of Fig. 13 which contained the spectra at different temperatures around the discotic/ isotropic liquid transition. On the other hand, no disappearance of the carbonyl structures occurred with simple phase transition. TTie disappearance of the carbonyl bands at 1730/1750 cm at the highest shear rate must therefore corresponds to a molecular realignment in which the dipole moment changes causing the infixed bands have been reoriented along the direction of observation. 

In ionic crystals, reconstruction effects can also be involved in the stabilization of polar surfaces (Tasker s type 3). For instance, the (100) surface of the fluorite-type crystal of Li20 becomes stable if half of the Li atoms are moved from the bottom face of the slab to the top face above the oxygen atoms to produce a zero-dipole structure (Figure 39). In fact, this kind of surface has been observed experimentally. ... 

Thus, in cubic oxyfluorides of niobium and tantalum with rock-salt (NaCl) crystal structures, the formation and extinction of spontaneous polarization occurs due to polar ordering or disordering of Li+ - Nb5+(Ta5+) dipoles. 

An irreversible extinction of the SHG signal at 150-200°C is observed for a number of other fluoride and oxyfluoride compounds of tantalum and niobium that crystallize in centrosymmetric space groups. This phenomenon is especially typical for the compounds prepared by precipitation from solutions [206]. The appearance of the weak SHG signal for such compounds is related to imperfections in their crystal structure and the creation of dipoles. Nevertheless, appropriate thermal treatment improves the structure and leads to the disappearance of dipoles and to the irreversible disappearance of the corresponding SHG signal. 

Figure 6-4. Qualitative energy level diagram of the 1 Bu excinm band structure of T<, at A =0 derived by the Ewald dipole-dipole sums for excitation light propagating along the a crystal axis.

In the operation of ferroelectric liquid crystal devices, the applied electric field couples directly to the spontaneous polarisation Ps and response times depend on the magnitude E Ps. Depending on the electronic structure (magnitude and direction of the dipole moment as well as position and polarity of the chiral species) and ordering of the molecules P can vary over several orders of magnitude (3 to 1.2 x 10 ), giving response times in the range 1-100 ps. 

The crystal structure of 4-butylphenyl-4 -butylbenzoyloxybenzoate was determined by Haase et al. [101]. The compound forms a nematic phase. The neighbouring phenyl rings of the molecule are twisted by 49 and 62°. The dipole moments of the carbonyloxy groups perpendicular to the long molecular axis are compensated to each other as much as possible. 

Kurogoshi and Hori [ 104] determined the crystal structures of the mesogenic ethyl and butyl 4-[4-(4-n-octyloxybenzoyloxy)benzylidene]aminobenzoates. The compounds have different phase sequences crystal-smectic A-nematic-isotropic and crystal-smectic C-smectic A-nematic-isotropic for the ethyl and butyl compounds, respectively. Both compounds have layer structures in the solid phase. The butyl compound contains two crystallographically independent molecules. Within the layers, adjacent molecules are arranged alternately so as to cancel their longitudinal dipole moments with each other. In the ethyl compound the core moieties are almost perpendicular to the layer plane, while in the butyl compound these moieties are tilted in the layer. 

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