Third-harmonic generation THG

Table 1 Coefficients for 7[ (a ) for third harmonic generation (THG), degenerate four wave mixing (DFWM), electric field induced second harmonic generation (ESHG), and Kerr effect in methane at the experimental geometry rcH = 2.052 a.u. A CCSD wavefunction and the t-aug-cc-pVDZ basis were used. (Results given in atomic units, the number in parentheses indicate powers of ten.)...

If we compare results obtained with the same basis sets with the three coupled cluster models CCS, CC2 and CCSD, we find similar trends as observed in Refs. [22,45] The CCS model underestimates strongly the static hyperpolarizabilities and their dispersion. The results are usually of similar quality as those obtained with SCF. For methane, the CCS static hyperpolarizabilities are intermediate between the SCF and the CCSD values obtained in the same basis set. In Ref. [45] the CCS percentage dispersion contribution to the third harmonic generation (THG) hyperpolarizability of methane was found to be slightly smaller than for SCF, both underestimating significantly the dispersion obtained with the correlated coupled cluster models CC2 and CCSD. Accordingly the CCS dispersion coeflBcients listed in Table 3 are substantially smaller than the respective CCSD results obtained in the same basis sets. 

Third-order susceptibilities of the PAV cast films were evaluated with the third-harmonic generation (THG) measurement [31,32]. The THG measurement was carried out at fundamental wavelength of 1064 nm and between 1500 nm and 2100 nm using difference-frequency generation combined with a Q-switched Nd YAG laser and a tunable dye laser. From the ratio of third-harmonic intensities I3m from the PAV films and a fused quartz plate ( 1 thick) as a standard, the value of x(3) was estimated according to the following equation derived by Kajzar et al. [33] ... 

The two important consequences of the third-order optical nonlinearities represented by x are third-harmonic generation and intensity dependence of the refractive index. Third-harmonic generation (THG) describes the process in which an incident photon field of frequency (oj) generates, through nonlinear polarization in the medium, a coherent optical field at 3a>. Through x interaction, the refractive index of the nonlinear medium is given as n = nQ+n I where n describes intensity dependence of the refractive index ana I is the instantaneous intensity of the laser pulse. There is no symmetry restriction on the third-order processes which can occur in all media including air. 

Third-Order NLO Techniques. There is a wider range of third-order techniques commonly used to characterize materials, including electric field induced second harmonic generation (EFISH) (15, 16), third harmonic generation (THG) (17) and degenerate four wave mixing (DFWM) (18). EFISH and DFWM will be discussed briefly then... 

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. 

This presentation is divided into two parts, one dealing with third harmonic generation (THG) non linear optical (NLO) materials and the other dealing with second harmonic generation (SHG) materials. 

By taking advantage of the deep penetration depth offered by CARS microscopy with near-infrared laser pulses, CARS tissue imaging has been demonstrated to complement other label-free optical techniques, such as auto-fluorescence that is limited to a few chemical species and optical tomography, second harmonic generation (SHG), and third harmonic generation (THG)... 

Equations (16) and (17) describe second-harmonic generation (SHG) and third-harmonic generation (THG) of one laser beam with a single polarization. Self-phase modulation (SPM) of a single laser beam is described in Eq.(18) as e.g. employed in z-scan experiments [6]. Equation (19) is the cross-phase modulation (XPM) process between two laser beams and Eq.(20) describes the four wave mixing with degenerate frequencies (DFWM). 

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. 

Table 9.3 Third harmonic generation (THG) and degenerate four wave mixing (DFWM) non-linear optical coefficients of conjugated polymers.

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