Nonlinear optical materials third-order effects

To conclude this article, it is hoped that the discussion of relevant issues and opportunities for chemists presented here will sufficiently stimulate the interest of the chemical community. Their active participation is vital for building our understanding of optical nonlinearities in molecular systems as well as for the development of useful nonlinear optical materials. It is the time now to search for new avenues other than conjugation effects to enhance third-order optical nonlinearities. Therefore, we should broaden the scope of molecular materials to incorporate inorganic and organometallic structures, especially those involving highly polarizable atoms. 

The fundamental component (aE) is linear in E and represents the linear optical properties discussed above. The second (jfiE-E) third ( yE-E-E) and subsequent harmonic terms are nonlinear in E and give rise to NTO effects. The / and values are referred to, respectively, as the first and second hyperpolarisabilities. The second harmonic term gives rise to second harmonic generation (SHG), the third results in frequency tripling effects, and so on. Importantly, since only the time-averaged asymmetrically induced polarisation leads to second-order NLO effects, the molecule and crystal must be non-centrosymmetric, otherwise the effects will cancel one another. Third-order effects, however, may be observed in both centrosymmetric and non-centrosymmetric materials. 

The possible variation of the material third-order susceptibility or nonlinear optical coefficients with particle size can originate from extrinsic effects, as the local field factor and metal concentration, or from intrinsic ones, that is from the size dependence of. Let us recall that, for Hache et al., the only size dependence of in the infraband contribution, due to quantum confinement... 

This work provides a relatively comprehensive review of studies involving ruthenium coordination and organometallic complexes as nonlinear optical (NLO) compounds/materials, including both quadratic (second-order) and cubic (third-order) effects, as well as dipolar and octupolar chromophores. Such complexes can display very large molecular NLO responses, as characterised by hyperpolarizabilities, and bulk effects such as second harmonic generation have also been observed in some instances. The great diversity of ruthenium chemistry provides an unparalleled variety of chromophoric structures, and facile Ru" —> Ru" redox processes can allow reversible and very effective switching of both quadratic and cubic NLO effects... 

The importance of the hyperpolarizability and susceptibility values relates to the fact that, provided these values are sufficiently large, a material exposed to a high-intensity laser beam exhibits nonlinear optical (NLO) properties. Remarkably, the optical properties of the material are altered by the light itself, although neither physical nor chemical alterations remain after the light is switched off. The quahty of nonlinear optical effects is cmciaUy determined by symmetry parameters. With respect to the electric field dependence of the vector P given by Eq. (3-4), second- and third-order NLO processes may be discriminated, depending on whether or determines the process. The discrimination between second- and third-order effects stems from the fact that second-order NLO processes are forbidden in centrosymmetric materials, a restriction that does not hold for third-order NLO processes. In the case of centrosymmetric materials, x is equal to zero, and the nonhnear dependence of the vector P is solely determined by Consequently, third-order NLO processes can occur with all materials, whereas second-order optical nonlinearity requires non-centrosymmetric materials. 

In Table 12.1, we list the effective nonlinear index coefficients 2 of these NLC materials along with other well-known classes of nonlinear optical materials 1. Note that is the equivalent third-order nonlinear susceptibility ot is the absorption... 

Combination with Static Fieids. A common technique, useful for optoelectronic devices, is to combine a monochromatic optical field with a DC or quasistatic field. This combination can lead to refractive index and absorption changes (linear or quadratic electrooptic effects and electroabsorption), or to electric-field induced second-harmonic generation (EFISH or DC-SHG, 2o) = co + co + 0) in a quasi-third-order process. In EFISH, the DC field orients the molecular dipole moments to enable or enhance the second-harmonic response of the material to the applied laser frequency. The combination of a DC field component with a single optical field is referred to as the linear electrooptic (Pockels) effect (co = co -I- 0), or the quadratic electrooptic (Kerr) effect ( = -I- 0 -I- 0). EFISH is discussed in this article, however, for the important role that it has played in the characterization of nonlinear optical materials for other applications. 

AH the properties dealt with up until now involve linear interactions between light and polymer. Interaction of li t with polymers in the nonlinear region involves second- and third-order effects as well as the phenomenon of photo refrac-tivity (56,57). An optical nonlinear optical (NIX)) polymer is one that, in response to an externally applied electric field, can either vary the speed of incoming light or alter its fi uency. Var3dng the speed of light involves a change in the reflective index of the material. An optically nonlinear polymer has two components the polymer itself and an optically nonlinear molecule (chromophore), which is either chemically attached to the polymer or dissolved in it. 

In an effort to identify materials appropriate for the appHcation of third-order optical nonlinearity, several figures of merit (EOM) have been defined (1—r5,r51—r53). Parallel all-optical (Kerr effect) switching and processing involve the focusing of many images onto a nonlinear slab where the transmissive... 

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 ... 

Third-Order Nonlinear Optical Effects in Molecular and Polymeric Materials... 

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