The wavelength dependence of the laser-induced photoacoustic signal amplitude has been measured for water dispersions of 10, 61, and 93 nm diameter gold nanospheres. The whole region of the localized surface plasmon resonance has been covered. This "photoacoustic excitation profile" can be overlayed with the extinction spectrum between 450 nm and 600 nm in the case of the smallest nanoparticles. At variance, the larger-sized nanoparticles display a progressive deviation from the extinction spectrum at longer wavelength, where the photoacoustic signal becomes relatively smaller. Considering that photoacoustics is intrinsically insensitive to light scattering, at least for optically thin samples, the results are in agreement with previous theoretical work predicting (i) an increasing contribution of scattering to extinction when the nanoparticle size increases and (ii) a larger scattering component at longer wavelengths. Therefore, the method has a general validity and can be applied to selectively determine light absorption by plasmonic systems.
Keywords: Gold nanoparticles; Laser excitation; Mie scattering; Photoacoustic spectroscopy.