Spectrally- and polarization-resolved hyper-Rayleigh scattering measurements with polarization-insensitive detection

Determination of the molecular first hyperpolarizability by hyper-Rayleigh scattering (HRS) is usually significantly complicated by a presence of the multiphoton excited fluorescence which has to be separated from HRS to obtain a meaningful values of the hyperpolarizability. We show, by performing a spectrally-resolved measurement, that the intensity and spectral shape of the fluorescence can depend strongly on the fundamental laser wavelength. Consequently, a properly selected excitation wavelength can significantly simplify the process of separation of HRS from the detected signal. We tested the developed experimental setup with a polarization-insensitive detection by measuring HRS generated in water and in aqueous solutions of 2-aminopyrimidine (AMP) and its monocation (HAMP). The effective hyperpolarizability of AMP and HAMP was measured experimentally and compared with that obtained by quantum chemical calculations. The polarization-resolved HRS measurement was performed for AMP and the experimentally obtained depolarization ratio agrees well with that predicted theoretically, which confirms that routine density functional theory computations of static hyperpolarizability tensor components can be considered as a sufficient approach suitable for non-interacting molecules dissolved in water.