Influence of two-photon absorption on third-order nonlinear optical processes as studied by degenerate four-wave mixing: The study of soluble didecyloxy substituted polyphenyls

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Abstract
We have investigated the influence of two-photon absorption on the third-order nonlinear optical properties of model organic molecules using the technique of degenerate four-wave mixing (DFWM). A theoretical formulation developed here shows that the presence of two-photon absorption, which is related to the imaginary part of the third-order susceptibility χ(3), leads to an enhancement of the effective third-order nonlinearity and to the appearance of effects caused by the formation of two-photon generated excited states. The dynamic behavior of the nonlinearity is then governed by the properties of excited molecules. The nonlinear effects also involve contributions which depend on the fifth power of the electric field. We have performed a systematic study of third-order nonlinear optical properties of alkoxy (–C10H21OCH) substituted p-polyphenyl oligomers using the technique of time-resolved degenerate four-wave mixing with subpicosecond pulses at 602 nm. Experimentally determined values of the second-order hyperpolarizability γ for the oligomers increase smoothly from the monomer to the trimer, with a more rapid increase to the pentamer and to the heptamer. In addition, the hyperpolarizabilities for the pentamer and the heptamer appear to be complex. A smooth increase of the γ value is expected from an increase of the π conjugation from a shorter chain oligomer to a longer chain oligomer. The more rapid increase of the γ value in the pentamer, and especially in the heptamer, however, cannot be explained satisfactorily by only taking into account the π-conjugation length. Two-photon absorption for the pentamer and the heptamer at the measurement wavelength of 602 nm is suggested to be important as the observed dynamic behavior is satisfactorily explained by the predictions of the theoretical model presented here. It is shown that the effective γ value for a two-photon absorbing material is a function of optical intensity, pulse width, and sample length if one uses the conventional degenerate four-wave mixing description.