Bulk materials, nonlinear optical

On the other hand, the nonlinear optical properties of nanometer-sized materials are also known to be different from the bulk, and such properties are strongly dependent on size and shape [11]. In 1992, Wang and Herron reported that the third-order nonlinear susceptibility, of silicon nanocrystals increased with decreasing size [12]. In contrast to silicon nanocrystals, of CdS nanocrystals decreased with decreasing size [ 13 ]. These results stimulated the investigation of the nonlinear optical properties of other semiconductor QDs. For the CdTe QDs that we are concentrating on, there have been few studies of nonresonant third-order nonlinear parameters. 

The systems discussed up to now all showed chiral susceptibilities that were of the same order of magnitude or smaller than the achiral susceptibility components. The system that we discuss in this section has chiral susceptibilities that dominate the nonlinear optical response.53 The material is a chiral helicenebisquinone derivative shown in Figure 9.22. In bulk samples, the nonracemic, but not the racemic, form of the material spontaneously organizes into long fibers clearly visible under an optical microscope. These fibers comprise columnar stacks of helicene molecules.54,55 Similar columnar stacks self-assemble in appropriate solvents, such as n-dodecane, when the concentration exceeds 1 mM. This association can be observed by a large increase in the circular dichroism (CD) of the solutions. 

The tutorial begins with a description of the basic concepts of nonlinear optics and presents illustrations from simple models to account for the origin of the effects. The microscopic or molecular origin of these effects is then discussed in more detail. Following this, the relationship between molecular responses and the effects observed in bulk materials are presented and finally some of the experimental methods used to characterize these effects are described. 

This paper is a tutorial overview of the techniques used to characterize the nonlinear optical properties of bulk materials and molecules. Methods that are commonly used for characterization of second- and third-order nonlinear optical properties are covered. Several techniques are described briefly and then followed by a more detailed discussion of the determination of molecular hyperpolarizabilities using third harmonic generation. 

In this paper it has been attempted to provide an introductory overview of some of the various nonlinear optical characterization techniques that chemists are likely to encounter in studies of bulk materials and molecular structure-property relationships. It has also been attempted to provide a relatively more detailed coverage on one topic to provide some insight into the connection between the macroscopic quantities measured and the nonlinear polarization of molecules. It is hoped that chemists will find this tutorial useful in their efforts to conduct fruitful research on nonlinear optical materials. 

Transition metal acetylides combine the properties of acetylenes with those of the transition metals, offering flexibility in the tuning of structural and electronic properties of both the organic and inorganic constituents. Optimization of the molecular and bulk crystalline properties is envisaged to lead to a new class of useful nonlinear optical materials. 

The EO effect is a second-order nonlinear optical (NLO) effect. Only non-centrosymmetrical materials exhibit second-order NLO effects. This non-centrosymmetry is a condition, both at the macroscopic level of the bulk arrangement of the material and at the microscopic level of the individual molecule. All electro-optic modulators that are presently used by telecom operators are ferro-electric inorganic crystals. The optical nonlinearity in these materials is to a large fraction caused by the nuclear displacement in the applied electric field, and to a smaller fraction by the movement of the electrons. This limits the bandwidth of the modulator. The nonlinear response of organic materials is purely electronic and, therefore, inherently faster. 

We have not failed to recognize that appropriately designed (6,0) carbon and C/B/N nanotubes may display considerably enhanced nonlinear optical activity. This term refers to the response of the dipole moment of a molecule (or the polarization of bulk material) to the oscillating electric field of electromagnetic radiation.82 85 The component of the dipole moment along an axis i in the presence of an electric field e can be represented by a Taylor series ... 

Phosphates showing a bulk polarization (i.e. ferroelectric phases) may be used for nonlinear optical processes see Nonlinear Optical Materials) such as second harmonic generation and electro-optic switching. KTP (Section 5.2.2) and related phases (NH4T10P04 and KTi0As04) are very efficient nonlinear materials. The ferroic phosphates described above also show nonlinear properties. KDP materials are inferior to KTP types but they find use in electro-optics as they are very transparent over a wide frequency range. 

The extensive jt-delocalized system of metal-dithiolene complexes is also responsible for the nonlinear optical properties (NLO) which have been recently reviewed . The interaction of radiation with the matter induces an instantaneous displacement (polarization Pq = /X = aE, where a is the linear polarizability) of the electronic density away from the nucleus at small field (linear optics). At high fields (laser light) the polarizability of the molecule can be driven beyond the linear regime and a nonlinear polarization is induced (NLO) = aE + fiE" + y E + and for the bulk material... 

Kuzyk, M. G. Relationship between the Molecular and the Bulk Response, Chapter 3 in Characterization Technu ues and Tabulations for Organic Nonlinear Optical Materials, Edited by M. G. Kuzyk, C. W. Dirk, Marcel Dekker. New York, 1998. 

Side-chain liquid-crystalline polymers with controlled molecular weights have been obtained by the polymerization of FM-25 with 1-22 (X = Br)/CuBr/ L-3 in the bulk at 100 °C, to examine the thermotropic transition as a function of the MWD.324 Second-order nonlinear optical materials with branched structure were prepared by the copper-catalyzed radical polymerization of FM-26 and FM-27 using hyperbranched poly[4-(chloromethyl)styrene] as a multifunctional initiator.325... 

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