Abstract

We present a tight-binding model for the linear and non-linear optical properties of small metal particles, which takes into account both size and matrix effects. We show that the surface states and the dielectric medium embedding the particles determine the properties of the microcrystals; in particular, we prove that the shallow-lyingd-band plays a crucial role in noble-metal particles. As an example, we calculate the third-order susceptibility and the phase-conjugated signalfor gold clusters made of several hundred atoms. A good agreement with experimental results is obtained.

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