Third harmonic generation properties

Fig. 8. Examples of some of the donor-acceptor substituted TEEs prepared for the exploration of structure-property relationships in the second- and third-order nonlinear optical effects of fully two-dimensionally-conjugated chromophores. For all compounds, the second hyperpolarizability y [10 esu], measured by third harmonic generation experiments in CHCI3 solution at a laser frequency of either A = 1.9 or 2.1 (second value if shown) pm is given in parentheses. n.o. not obtained...

The unique properties of liquid crystals have also provided opportunity for study of novel nonlinear optical processes. An example involves the ability to modify the pitch of cholesteric liquid crystals. Because a pseudo-wave vector may be associated with the period of pitch, a number of interesting Umklapp type phasematching processes (processes in which wave vector conservation is relaxed to allow the vector addition to equal some combination of the material pseudo-wave vectors rather than zero) are possible in these pseudo-one-dimensional media. Shen and coworkers have investigated these employing optical third harmonic generation (5.) and four-wavemixing (6). 

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. 

Characterization of Molecular Hyperpolarizabilities Using Third Harmonic Generation. Third harmonic generation (THG) is the generation of light at frequency 3co by the nonlinear interaction of a material and a fundamental laser field at frequency co. The process involves the third-order susceptibility x 3K-3 , , ) where —3 represents an output photon at 3 and the three s stand for the three input photons at . Since x(3) is a fourth (even) rank tensor property it can be nonzero for all material symmetry classes including isotropic media. This is easy to see since the components of x(3) transform like products of four spatial coordinates, e.g. x4 or x2y2. There are 21 components that are even under an inversion operation and thus can be nonzero in an isotropic medium. Since some of the terms are interrelated there are only four independent terms for the isotropic case. 

Examples of studies on multiphoton absorption processes and nonlinear second-and third-harmonic generation processes will be discussed along with some possible radiative and nonradiative processes. The selection rules for multiphoton absorption will be mentioned in Section 7.3, and molecular examples will be shown along with their correlating photophysical properties in Section 7.4. The effect of some parameters relating to second-order activity along the lanthanide... 

LeBozec and co-workers have reported nonlinear behavior in a series ofterpyri-dyl and dipicolinic acid complexes, with further studies on these complexes by Maury and co-workers [83, 84]. Their research was on new molecular materials for optoelectronics, with studies based on octupolar nonlinear optical molecules showing that molecular quadratic hyperpolarizability values were strongly influenced by the symmetry of the complexes [85]. Other studies on organic-lanthanide complexes with nonlinear optics have also reported second- and third-harmonic generation behavior with simultaneous multiphoton absorption properties [50]. Such studies have shown the importance of coordination chemistry as a versatile tool in the design of nonlinear materials. 

While the above discussion clearly highlights the importance of including solvent effects in the calculations, the calculated properties cannot be compared directly with experimental results. This is mainly caused by the many different conventions used for representing hyperpolarizabilities and susceptibilities. However, the calculated properties can be combined with appropriate, calculated Lorentz/Onsager local field factors to obtain macroscopic susceptibilities that can be compared with experimental results. For water, we used this to calculate the refractive index and the third harmonic generation (THG) and the electric field-induced second harmonic (EFISH) non-linear susceptibilities. The results are collected in Table 3-11. 

Another potential application of fully converted polydiacetylenes is based upon their unusual non-linear optical properties. Sauteret et al. found that the third order susceptibilities of TCDU and TS increases by about a factor of 600 upon polymerization and become comparable to those of inorganic semiconductors like GaAs or germanium. This is a consequence of the increase of n-electron delocalization upon polymerization. Polymeric diacetylenes can therefore be used as efficient elements for third harmonic generation. In Ref. this effect has been employed for tripling the frequencies of 1.89 pm and 2.62 pm radiation. 

The influence of the substituent at tlie periphery of the macrocycle on the NLO properties was studied in solution. Thus, various subphthalocyanines bearing representative electron-donor or acceptor groups were synthesized and their NLO properties were measured employing HRS, EFISH and Third Harmonic Generation (THG) methods [62, 63]. 

The nonlinear optical properties of rotaxanes and catenanes were studied mainly by three techniques the optical second and third harmonic generation and the electro-optic Kerr effect. As already mentioned, the harmonic generation techniques give the fast, electronic in origin, molecular and bulk hyperpolarizabili-ties, whereas the electro-optic methods are sensitive to all effects which induce optical birefringence, such as e.g. the rotation of molecules. Therefore the last technique is very useful to study the rotational mobility of molecules and/or their parts. 

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