Hyper-Rayleigh scattering of gold nanorods and their relationship with linear assemblies of gold nanospheres

The surface plasmon enhanced hyper-Rayleigh scattering light collected from an aqueous solution of gold nanorods is reported. A non negligible part of the signal is attributed to a photoluminescence background attributed to the electron hole recombination following multiphoton excitation of d-valence band electrons into the sp-conduction band. This radiative relaxation process is likely favored by the presence of the organic species adsorbed at the surface of the nanorods. The absolute value for the hyperpolarisability of nanorods is also compared by the external reference method to that of para-nitroaniline and found to be rather large although an absolute value cannot be given because the exact number density of the gold nanorods is unaccessible. This value is however compared with values reported for linear assemblies of gold spherical nanoparticles and further support the simple model of gold metal ellipsoids to describe the hyper-Rayleigh light intensities. The polarisation analysis of the hyper-Rayleigh scattering light is also determined for gold nanorods and compared to the expected one for gold nanospheres. For the latter spheres, the weakness of the signal intensities precludes a definite comparison with the model. On the opposite, for the nanorods, the polarisation dependence of the hyper-Rayleigh scattered light clearly deviates from the one expected for nanospheres.