Measuring the molecular second hyperpolarizability in absorptive solutions by the third harmonic generation ratio technique

Measurement of the second hyperpolarizability (γ) values of compounds can provide insight into the molecular structural requirements for enhancement of third harmonic generation (THG) signal. A convenient method for measuring the γ of compounds in solutions was developed by implementing the THG ratio method which is based on measuring the THG intensity from two interfaces using a nonlinear optical microscope while accounting for the refractive index of solutions at the fundamental and third harmonic wavelengths. We demonstrated that the difference in refractive index at both wavelengths strongly influenced the calculation of γ values when compounds have absorption near the third harmonic or fundamental wavelength. To this end, a refractometer with the wavelength tuning range from UV to near IR was constructed, and the measured refractive indices were used to extract the γ values. The γ values of carotenoids and chlorophylls found in photosynthetic pigment–protein complexes were explored. Large differences in the refractive index at third harmonic and fundamental wavelengths for chlorophylls result in γ values that are more than two orders of magnitude larger than γ values for carotenoids as well as the sign of chlorophylls’ γ values is negative while carotenoids have positive γ values.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Second hyperpolarizability (γ) measured with THG ratio technique. ► γ determination with concentrations as low as μM have been achieved. ► Refractive indices are measured with a home-built UV-near IR tunable refractometer. ► Measured carotenoids have positive γ values and chlorophylls negative γ values. ► Opposite signs of γ lead to interesting implications for photosynthetic complexes.