Noncentrosymmetric requirements

For second-order NLO applications, the films need to be noncentrosymmetric. 4-Di(2-hydroxyethyl)amino-4 -a2oben2enephosphonate was used to form SAMs on 2irconium-treated phosphorylated surfaces. Further reaction with POCl and hydrolysis created a new phosphorylated surface that could be treated with 2irconium salt (341—343). The principal advantage of the phosphate systems is high thermal stabiUty, simple preparation, and the variety of substrates that can be used. The latter is especially important if transparent substrates are required. Thiolate monolayers are not transparent, and alkyltrichlorosilanes have a serious stabiUty disadvantage. 

Optical second harmonic generation (SHG), which is the conversion of two photons of frequency u to a single photon of frequency 2co, is known to be an inherently surface-sensitive technique, because it requires a noncentrosymmetrical medium. At the interface between two centrosymmetrical media, such as the interface between two liquids, only the molecules which participate in the asymmetry of the interface will contribute to the SHG [18]. SHG has been used as an in-situ probe of chemisorption, molecular orientation, and... 

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. 

A specific set of experiments which must be mentioned, being directly associated with the main topic of this paper, is the work of Bergman, et. al. (22) dealing with the second-order nonlinear optical properties of polyvinylidene fluoride (PVF2). Nonvanishing the second-order nonlinear electric dipole susceptibility, is expected in PVF2 since it exhibits other properties requiring noncentrosymmetric microscopic structure. These properties appear... 

For the practical application to nonlinear optics, further, noncentrosymmetric LB films are required to possess not only large nonlinear optical response but excellent optical quality and thickness appropriate to optical devices. In this study, a family of pyrazine derivatives was found to be an LB film-forming material applicable to waveguide devices. The optical nonlinearity in the pyrazine LB films and the application of the pyrazine LB films to a frequency-doubling waveguide device is demonstrated in the latter part. 

In order to bridge the gap between an SHG-active material and one optimized for use in an optoelectronic device, many compounds have been synthesized, characterized, modified and then ultimately rejected during the past decade (i-3). This is not surprising, since the ideal material must fulfil a plethora of stringent requirements (4-7). The most critical condition for an SHG-active material is that it must form noncentrosymmetric structures however, thermal stability, in volatility, transparency, lack of colour, mechanical strength and crystal habit are also crucial properties for materials to be incorporated into practical devices. 

Answering this question involves an examination of Equation (12). The largest QEO nonlinearities are available when the QEO probe frequency, co, is close to resonance. This is the restriction that can potentially allow the two-level model to be applicable. Note that the two-level model depends on the competition between yc and yn, which have opposite sign. It is important to note that under centrosymmetry, yc should be the only contribution to yqeo> while the yqeo for noncentrosymmetric molecules consists of yc+yn. A first order correction to this model will require the additional term yfp. It is important to judge what effect this term may have on this speculation and the potential interpretation. In general, it should be to lower (However, note as in the case of frans-octatetraene,... 

Clearly, a requirement for device quality second-order nonlinear optical materials is a noncentrosymmetric dipolar chromophore lattice. There are several ways by which such lattices have been achieved. With all methods, a force must... 

In resonant infrared multidimensional spectroscopies the excitation pulses couple directly to the transition dipoles. The lowest order possible technique in noncentrosymmetrical media involves three-pulses, and is, in general, three dimensional (Fig. 1A). Simulating the signal requires calculation of the third-order response function. In a small molecule this can be done by applying the sum-over-states expressions (see Appendix A), taking into account all possible Liouville space pathways described by the Feynman diagrams shown in Fig. IB. The third-order response of coupled anharmonic vibrations depends on the complete set of one- and two-exciton states coupled to thermal bath (18), and the sum-over-states approach rapidly becomes computationally more expensive as the molecule size is increased. 

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. 

Construction of a bulk material possessing a large bulk susceptibility requires not only molecular constituents with large microscopic susceptibilities but a noncentrosymmetric system where the orientation of the molecular species results in additivity of the molecular susceptibilities. 

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,... 

Thus, in both cases, the molecular unit can be tailored to meet a specific requirement. A second crucial step in engineering a molecular structure for nonlinear applications is to optimize the crystal structure. For second-order effects, a noncentrosymmetrical geometry is essential. Anisotropic features, such as parallel conjugated chains, are also useful for third-order effects. An important factor in the optimization process is to shape the material for a specific device so as to enhance the nonlinear efficiency of a given structure. A thin-film geometry is normally preferred because nonlinear interactions, linear filtering, and transmission functions can be integrated into one precise monolithic structure. 

When crystals are noncentrosymmetric, the situation becomes more complicated because there are two possible phases angles that are derived for each reflection for data from one isomorphous pair. Therefore, in order to derive the phase angle, more than one isomorphous pair is required. This problem was first tackled by Johannes M. Bijvoet, Cornells Bokhoven and Jean C. Schoone, who solved the noncentrosymmetric isomorphous structures of strychnine sulfate and selenate. ... 

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