Nonlinear optical polarization

Optically active polymers are potentially very useful in areas such as asymmetric catalysis, nonlinear optics, polarized photo and electroluminescence, and enantioselective separation and sensing.26 Transition metal coupling polymerization has also been applied to the synthesis of these polymers.27 For example, from the Ni(II)-catalyzed polymerization, a regioregular head-to-tail polymer 32 was obtained (Scheme 9.17).28 This polymer is optically active because of the optically active chiral side chains. 

Over the past decade it has been learned that organic materials containing appropriately constituted or substituted conjugation systems may exhibit highly enhanced electronic nonlinear optical polarization responses Since the microscopic second-order... 

Thus, just as linear polarizabilities are frequency dependent, so are the nonlinear polarizabilities. Perhaps it is not surprising that most organic materials, with almost exclusively electronic nonlinear optical polarization, have similar efficiencies for SHG and the LEO effect. In contrast, inorganic materials, such as lithium niobate, in which there is a substantial vibrational component to the nonlinear polarization, are substantially more efficient for the LEO effect than for SHG. 

Chang YJ, Castner Jr. EW. The intermolecular dynamics of substituted benzene and cyclohexane liquids, studied by femtosecond nonlinear-optical polarization spectroscopy. J Phys Chem 1996 100 3330-3343. 

The surface nonlinear optical polarization of second order can be written in the form [34]... 

Sepulveda, M.A., Mukamel, S. Semiclassical theory of molecular nonlinear optical polarization. J. Chem. Phys. 102, 9327-9344 (1995)... 

A diagrannnatic approach that can unify the theory underlymg these many spectroscopies is presented. The most complete theoretical treatment is achieved by applying statistical quantum mechanics in the fonn of the time evolution of the light/matter density operator. (It is recoimnended that anyone interested in advanced study of this topic should familiarize themselves with density operator fonnalism [8, 9, 10, H and f2]. Most books on nonlinear optics [13,14, f5,16 and 17] and nonlinear optical spectroscopy [18,19] treat this in much detail.) Once the density operator is known at any time and position within a material, its matrix in the eigenstate basis set of the constituents (usually molecules) can be detennined. The ensemble averaged electrical polarization, P, is then obtained—tlie centrepiece of all spectroscopies based on the electric component of the EM field. 

Further subclassification of nonlinear optical materials can be explained by the foUowiag two equations of microscopic, ie, atomic or molecular, polarization,, and macroscopic polarization, P, as power series ia the appHed electric field, E (disregarding quadmpolar terms which are unimportant for device appHcations) ... 

Fig. 1. Representative device configurations exploiting electrooptic second-order nonlinear optical materials are shown. Schematic representations are given for (a) a Mach-Zehnder interferometer, (b) a birefringent modulator, and (c) a directional coupler. In (b) the optical input to the birefringent modulator is polarized at 45 degrees and excites both transverse electric (TE) and transverse magnetic (TM) modes. The appHed voltage modulates the output polarization. Intensity modulation is achieved using polarizing components at the output.

Crystals with one of the ten polar point-group symmetries (Ci, C2, Cs, C2V, C4, C4V, C3, C3v, C(, Cgv) are called polar crystals. They display spontaneous polarization and form a family of ferroelectric materials. The main properties of ferroelectric materials include relatively high dielectric permittivity, ferroelectric-paraelectric phase transition that occurs at a certain temperature called the Curie temperature, piezoelectric effect, pyroelectric effect, nonlinear optic property - the ability to multiply frequencies, ferroelectric hysteresis loop, and electrostrictive, electro-optic and other properties [16, 388],... 

The asymmetrical D-ji-A dyes, often referred to as push-pull polyenes, are an additional class of cyanine-like molecules of interest. Due to their dipolar nature, the linear and nonlinear optical properties of this series of dyes can be strongly influenced by solvent polarity [84]. The structures of a series of such dyes (G19,... 

Based on the fundamental dipole moment concepts of mesomeric moment and interaction moment, models to explain the enhanced optical nonlinearities of polarized conjugated molecules have been devised. The equivalent internal field (EIF) model of Oudar and Chemla relates the j8 of a molecule to an equivalent electric field ER due to substituent R which biases the hyperpolarizabilities (28). In the case of donor-acceptor systems anomalously large nonlinearities result as a consequence of contributions from intramolecular charge-transfer interaction (related to /xjnt) and expressions to quantify this contribution have been obtained (29). Related treatments dealing with this problem have appeared one due to Levine and Bethea bearing directly on the EIF model (30), another due to Levine using spectroscopically derived substituent perturbations rather than dipole moment based data (31.) and yet another more empirical treatment by Dulcic and Sauteret involving reinforcement of substituent effects (32). 

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