Acentric materials

Acceptor species concentrations, equations, 400-401 Acentric materials biomimetic design, 454-455 synthesis approaches, 446 Ar-(2-Acetamido-4-nitrophenyl)pyrrolidene control of crystal polymorphism with assistance of auxiliary, 480-482 packing arrangements, 480,481-482/ Acetylenes, second- and third-order optical nonlinearities, 605-606 N-Acetyltyrosine, phase-matching loci for doubling, 355,356/, t Acid dimers, orientations, 454 Active polymer waveguides, applications, 111... 

LB films are good candidate materials for exhibiting ferro-, pyro- and piezoelectric properties. Such behaviour requires a macroscopically polar structure normally inherent in acentric materials. Y-type LB films are unable to exhibit such properties, since these materials possess a centre of symmetry. LB films deposited by the X- or Z-type mode are therefore required, or combinations of different materials deposited alternately in the Y-type mode will also give AB-type multilayers having an overall macroscopic polarity. 

Panunto, T. W., Urbanczyk-Lipkowska, Z., Johnson, R., and Etter, M. C., Hydrogen-bond formation in nitroanilines the first step in designing acentric materials, J. Am. Cherru Soc.,... 

Typical electrostrictive materials include such compounds as lead manganese niobate lead titanate (PMN PT) and lead lanthanium 2irconate titanate (PLZT). Electrostriction is a fourth-rank tensor property observed in both centric and acentric insulators (14,15). 

A simple calculation for urea by Spackman is instructive. Urea crystallizes in an acentric space group (it is a well-known nonlinear optical material), in which the symmetry axes of the molecules coincide with the two-fold axes of the space group. All molecules are lined up parallel to the tetragonal c axis. If the electric field is given by E, and the principal element of the diagonalized molecular polarizability tensor along the c axis by oc , the induced moment along the polar c axis is... 

Using polar chains and polar arrays to bias the formation of acentric bulk materials is a promising and potentially useful approach to designing acentric solids, but is somewhat unsatisfying because the nature of the bias is not well understood and is thus not easy to control. In searching for a more definitive and logical mechanism for preparing acentric bulk materials, we have borrowed one of nature s tricks. 

Of the thirty-two crystal classes, twenty-two lack an inversion center and are therefore known as non-centrosymmetric, or acentric. Crystalline and polycrystalline bulk materials that belong to acentric crystal classes can exhibit a variety of technologically important physical properties, including optical activity, pyroelectricity, piezoelectricity, and second-harmonic generation (SHG, or frequency doubling). The relationships between acentric crystal classes and physical properties of bulk materials are summarized in Table 9.1.1. 

Eleven acentric crystal classes are chiral, i.e., they exist in enantiomorphic forms, whereas ten are polar, i.e., they exhibit a dipole moment. Only five (1,2, 3, 4, and 6) have both chiral and polar symmetry. All acentric crystal classes except 432 possess the same symmetry requirements for materials to display piezoelectric and SHG properties. Both ferroelectricity and pyroelectricity are related to polarity a ferroelectric material crystallizes in one of ten polar crystal classes (1, 2, 3,4, 6, m, mm2, 3m, 4mm, and 6mm) and possesses a permanent dipole moment that can be reversed by an applied voltage, but the spontaneous polarization (as a function of temperature) of a pyroelectric material is not. Thus all ferroelectric materials are pyroelectric, but the converse is not true. 

Table 9.1.1. Physical properties of materials found in acentric crystal classes...

Assessing thermal and photochemical stability is important. Thermal stability can be readily measured by measuring properties such as second harmonic generation as a function of heating at a constant rate (e.g., 4-10 °C/min) [121]. The temperature at which second-order optical nonlinearity is first observed to decrease is taken as defining the thermal stability of the material [2,3,5,63,63]. It is important to understand that the loss of second-order nonlinear optical activity measured in such experiments is not due to chemical decomposition of the electro-optic material but rather is due to relaxation of poling-induced acentric... 

In particular, if the molecule has no center of symmetry and the crystal is in an acentric space group, then only the even-order susceptibilities x<2>> x (and the corresponding molecular dipole moment /r0 and the even-order hyperpolarizabilities j8, 8, etc.) are nonzero. For all materials, regardless of symmetry, the odd-order molecular moments (a, y, etc.) and susceptibilities 0r(1), X ) can be nonzero. 

The work reported here has shown that inclusion complexation of organic and organometallic chromophores by thiourea, TOT and cyclodextrins can induce second harmonic generation capability in the polar crystals which result, even when the original bulk materials are themselves incapable of SHG. Structural evidence has been presented to show tht the solid state inclusion structures are acentric, and a simple electronic picture t0 the polarization response of these materials within the two-state modeP ° has been discussed. In an earlier section we remarked that of the many complexes we have made, only one has NOT been acentric. This result was not anticipated. We postulate that it is a natural tendancy in such materials, rather that an exception. If we consider a dipolar molecule in isotropic solution, we can imagine that if it were to aggregate, it would do so in a head to tail fashion in order to minimize electrostatic repulsion. The situation is illustrated in Scheme 3. The arrangement that would result is centrosymmetric. 

---