Second-harmonic generation corrections

The CCSD model gives for static and frequency-dependent hyperpolarizabilities usually results close to the experimental values, provided that the effects of vibrational averaging and the pure vibrational contributions have been accounted for. Zero point vibrational corrections for the static and the electric field induced second harmonic generation (ESHG) hyperpolarizability of methane have recently been calculated by Bishop and Sauer using SCF and MCSCF wavefunctions [51]. 

We have listed the hrst three of the six experiments (a-c) below. Arrange them in order of complexity (and, hence, the order in which they will be performed), identifying the correct ordinal language (hrst, second, third) where indicated. (SHG = second harmonic generation SAM = self-assembled monolayer.)... 

After an overview of the main papers devoted to chaos in lasers (Section I.A) and in nonlinear optical processes (Section I.B), we present a more detailed analysis of dynamics in a process of second-harmonic generation of light (Section II) as well as in Kerr oscillators (Section III). The last case we consider particularly in the context of coupled nonlinear systems. Finally, we present a cumulant approach to the problem of quantum corrections to the classical dynamics in second-harmonic generation and Kerr processes (Section IV). 

Hiis polarizability is measured by electric-field-induced second-harmonic generation (EFISHG). Again, local field corrections for the optical fields do not yield the second-order polarizability j8 of the free molecule but rather the solute polarizability /3 which contains a contribution induced by the static... 

All applications quoted so far were for the linear response. Very few investigations have dealt with the higher-order response described in Sect. 5.2. The frequency-dependent third-order hyperpolarizabilities of rare-gas atoms were calculated by Senatore and Subbaswamy [86] within the ALDA the calculated values turned out to bee too large by a factor of two, further indicating the need for self-interaction corrected functionals in the calculation of response properties. The effect of adsorbates on second-harmonic generation at simple metal surfaces was invested by Kuchler and Rebentrost [205, 206]. Most recently, the second-order harmonic generation in bulk insulators was calculated within the ALDA [207]. 

Tabic 4 shows results from [36] for the static and the second harmonic generation hyperpolarizabilities of CO at 694.3 nm. The electronic contributions were obtained from CC3/d-aug-cc-pVTZ calculations carried out at R q = 2.132bohr. These were approximately corrected for remaining basis set errors by adding the difference between CCSD/d-aug-cc-pVQZ and CCSD/d-aug-cc-pVTZ results for the same frequency and internuclear distance. For CO the triples correction for /3 (0) is 1.72 a.u. or =6%. At a wavelength of 694.3 nm the triples correction is already 2.35 a.u. or s7%. Thus, there is in tliis case a notable triples effect on the frequency dispersion. Since there is no information available about correlation contributions beyond CC3, it is difficult to assess the accuracy of these results. 

However, as we noted earlier (in Section II), it is most important to have a full temporal and spatial profile of the picosecond laser pulses in order to correctly interpret the one or two photon excited molecular response functions (absorption, emission, Raman scattering) of the system under study. While autocorrelation techniques such as second harmonic generation (SHG) or two photon fluorescence have always been the route to such short pulse measurements, a significant advance has recently been made in bringing these conventional autocorrelation measurements into the real-time domain. ... 

Furthermore, they examined the performance of different density functionals, including a local-density approximation and a generalized-gradient approximation as well as the functional of van Leeuwen and Baerends that has been constructed to have the correct asymptotic behaviour. Moreover, they considered different frequency-dependent processes, including third-harmonic generation [THG, corresponding to y( 3electric-field-induced second harmonic generation (EFISH, y( 2electro-optic Kerr effect [EOKO, y(—ft> optical rectification [OR, /S(0 [Pg.161]

Bishop, D. M. and Sauer, S. P. A. (1997). Calculation, with the inclusion of vibrational corrections, of the DC-electric-field induced second-harmonic-generation hyperpolarizability of methane. J. Chem. Phys., 107, 8502-8509. 

Quinet, O., Champagne, B., and Kirtman, B. (2003) Zero-point vibrational averaging correction for second harmonic generation... 

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