Mechanisms of resonant low frequency Raman scattering from metallic nanoparticle Lamb modes

The low frequency Raman scattering from gold nanoparticle bimodal assemblies with controlled size distributions has been studied. Special care has been paid to determining the size dependence of the Raman intensity corresponding to the quadrupolar Lamb mode. Existing models based on a microscopic description of the scattering mechanism in small particles (bond polarizability, dipole induced dipole models) predict, for any Raman-active Lamb modes, an inelastic intensity scaling as the volume of the nanoparticle. Surprisingly experimental intensity ratios are found to be anomalously much greater than theoretical ones, calling into question this scaling law. To explain these discrepancies, a simple mechanism of Raman scattering, based on the density fluctuations in the nanoparticles induced by the Lamb modes, is introduced. This modeling, in which the nanoparticle is described as an elastic isotropic continuous medium-as in Lamb theory, successfully explains the major features exhibited by low frequency Raman modes. Moreover this model provides a unified picture for any material, suitable for handling both small and large size ranges, as well as non-resonant and resonant excitation conditions in the case of metallic species.