Noncentrosymmetric symmetry

To overcome volatility problems, two-photon absorption (TPA) is the most promising long-term data storage technique to date. TPA can be observed in all materials and lacks the noncentrosymmetric symmetry requirements of even-order nonlinear optical effects. Nevertheless, in centrosymmetric polymers two-photon absorption is allowed between states that have the same parity according to parity selection rules (112). Such a system has been demonstrated with nondestructive readout (113). Additionally, use of two-photon absorption on photorefractive polymer dispersed liquid crystals has been used to record a high 3D data density of 204.8 Gbits/cm (158). 

Optical second-harmonic generation (SHG) has recently emerged as a powerful surface probe [95, 96]. Second harmonic generation has long been used to produce frequency doublers from noncentrosymmetric crystals. As a surface probe, SHG can be caused by the break in symmetry at the interface between two centrosymmetric media. A high-powered pulsed laser is focused at an angle of incidence from 30 to 70° onto the sample at a power density of 10 to 10 W/cm. The harmonic is observed in reflection or transmission at twice the incident frequency with a photomultiplier tube. 

The first and third order terms in odd powers of the applied electric field are present for all materials. In the second order term, a polarization is induced proportional to the square of the applied electric field, and the. nonlinear second order optical susceptibility must, therefore, vanish in crystals that possess a center of symmetry. In addition to the noncentrosymmetric structure, efficient second harmonic generation requires crystals to possess propagation directions where the crystal birefringence cancels the natural dispersion leading to phase matching. 

Noncentrosymmetric achiral crystals of monoclinic point symmetry m and of orthorhombic point symmetry mm2 are also appropriate for determination of the absolute configuration of chiral resolved additives. For the point group m, only the left or right halves of Schemes 13a are relevant. In such an arrangement,... 

Orthorhombic symmetry mm2 comprises two mirror planes perpendicular to each other, which automatically generates a twofold axis along the line of intersection. This point symmetry applies to all noncentrosymmetric orthorhombic crystals that have mirror or glide planes such as those of space groups Pna2t and Pca2,. 

Ferroelectrics. Among the 32 crystal classes, 11 possess a centre of symmetry and are centrosymmetric and therefore do not possess polar properties. Of the 21 noncentrosymmetric classes, 20 of them exhibit electric polarity when subjected to a stress and are called piezoelectric one of the noncentrosymmetric classes (cubic 432) has other symmetry elements which combine to exclude piezoelectric character. Piezoelectric crystals obey a linear relationship P,- = gijFj between polarization P and force F, where is the piezoelectric coefficient. An inverse piezoelectric effect leads to mechanical deformation or strain under the influence of an electric field. Ten of the 20 piezoelectric classes possess a unique polar axis. In nonconducting crystals, a change in polarization can be observed by a change in temperature, and they are referred to as pyroelectric crystals. If the polarity of a pyroelectric crystal can be reversed by the application on an electric field, we call such a crystal a ferroelectric. A knowledge of the crystal class is therefore sufficient to establish the piezoelectric or the pyroelectric nature of a solid, but reversible polarization is a necessary condition for ferroelectricity. While all ferroelectric materials are also piezoelectric, the converse is not true for example, quartz is piezoelectric, but not ferroelectric. 

In (a) the ion is so situated as to be in a noncentrosymmetric field, even when it is not vibrating. In this case electric-dipole emission is allowed. In (b) there is inversion symmetry when the ion is not vibrating, but vibration carried it to some other point Py at which the center of symmetry is lost. It should be self-evident that, even when the ion is in a noncentrosymmetric environment, vibrations may be important. That is, changes in the crystal-field symmetry induced by the vibronic motion will lead to violations of the crystal-field-selection rules. 

The crystal structure of Compound 4, which was found to possess a centro-symmetric triclinic unit cell containing six tetraphenylarsonium cations, two [Nii2(CO)2iH]3 trianions, and two solvent acetone molecules, also was solved by the combined Patterson-Fourier method, based on the assumption of the dodecanickel core of the trianion being analogous to that of the dianion. Peaks corresponding to all of the nickel and arsenic atoms were first located from successive Fourier syntheses in the unit cell under noncentrosymmetric PI symmetry, after which initial atomic coordinates for the 12 independent nickel and three independent arsenic atoms were obtained by an origin shift to an approximate center of symmetry relating pairs of these peaks to one another. 

Second-order optical nonlinearities result from introduction of a cubic term in the potential function for the electron, and third-order optical nonlinearities result from introduction of a quartic term (Figure 18). Two important points relate to the symmetry of this perturbation. First, while negative and positive p both give rise to the same potential and therefore the same physical effects (the only difference being the orientation of the coordinate system), a negative y will lead to a different electron potential than will a positive y. Second, the quartic perturbation has mirror symmetry with respect to a distortion coordinate as a result, both centrosymmetric and noncentrosymmetric materials will exhibit third-order optical nonlinearities. If we reconsider equation 23 for the expansion of polarization of a molecule as a function of electric field and assume that the even-order terms are zero (i.e., that the molecule is centrosymmetric), we see that polarization at a given point in space is ... 

The search for efficient NLO-phores includes also the design of octupolar derivatives [40, 70a]. The advantages associated with this alternative class of NLO-phore include an improved nonlinearity-transparency trade-off and more facile noncentrosymmetric arrangement in the solid state due to the absence of dipolar moments. To this end, the 3-D chromophores 135 and 136 with C3 and D2 (approximate T) symmetry, respectively (Scheme 4.39), have been prepared according to classical synthetic routes [73a]. 

For noncentrosymmetric space groups, the point with the highest site symmetry and lowest multiplicity is chosen as the origin. This means that either the Ti atom or the Ca atom could be chosen as the origin since they both have the same multiplicity (one-fold) and site symmetry m3m). However, it is important to note that the Ca and Ti atom are not at the same position. The Bravais lattice is primitive, as indicated by the space group symbol. Therefore, if we allow the Ti atom positions to coincide with lattice points, the Ca atoms and O atoms cannot. 

A centrosymmetric stress cannot produce a noncentrosymmetric polarization in a centrosymmetric crystal. Electric dipoles cannot form in crystals with an inversion center. Hence, only the twenty noncentrosymmetric point groups are associated with piezoelectricity (the noncentrosymmetric cubic class 432 has a combination of other symmetry elements which preclude piezoelectricity). The piezoelectric strain coefficients, dj for these point groups are given in Table 8.7, where, as expected, crystal symmetry dictates the number of independent coefficients. For example, triclinic crystals require the full set of 18 coefficients to describe their piezoelectric properties, but mono-chnic crystals require only 8 or 10, depending on the point group. 

For a centrosymmetric structure, Uhki can equal only 0 or 180° (i.e. F having signs + or respectively), for a noncentrosymmetric structure it can have any value. Owing to the translational symmetry of crystals, p xyz) can be considered as a periodic function in three-dimensional space and expressed by the Fourier transform of equation (8),... 

The dipole moment operator ( x) has associated with it ungerade character so the integral will be zero if v i[ and v g are both either gerade or ungerade. Again, Laporte-forbidden transitions do occur (with 10 -10 the intensity of fully allowed transitions) because of mixing of the orbitals in the excited state in noncentrosymmetric sites, and even in centrosym-metric sites as a result of vibrations of the metal atoms away from the center of symmetry (vibronic coupling). 

In this equation, po is the permanent dipole moment of the molecule, a is the linear polarizability, 3 is the first hyperpolarizability, and 7 is the second hyperpolarizability. a, and 7 are tensors of rank 2, 3, and 4 respectively. Symmetry requires that all terms of even order in the electric field of the Equation 10.1 vanish when the molecule possesses an inversion center. This means that only noncentrosymmetric molecules will have second-order NLO properties. In a dielectric medium consisting of polarizable molecules, the local electric field at a given molecule differs from the externally applied field due to the sum of the dipole fields of the other molecules. Different models have been developed to express the local field as a function of the externally applied field but they will not be presented here. In disordered media,... 

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