The femtosecond optical response of noble metal nanoparticles and its connection to the ultrafast electron dynamics are discussed in light of the results of high-sensitivity femtosecond pump-probe experiments. The physical origins of the nonlinear responses in the vicinity of the surface plasmon resonance and interband transition threshold are analyzed using extension of the theoretical models used in the bulk materials. These responses contain information on the electron interaction processes (electron-electron and electron-phonon scattering) that can thus be directly investigated in the time domain. Their size and environment dependences are discussed, and the results are compared to the ones in the bulk materials. Time-resolved techniques also permit direct study of the vibrational modes of metal nanoparticles and, in particular, the determination of their damping, which is a sensitive probe of the nature of the surrounding matrix and of the interface quality.

Electron-electron and electron-lattice interactions in noble metals are discussed in the light of two-color femtosecond pump-probe measurements in silver films. The internal thermalization of a nonequilibrium electron distribution created by intraband absorption of a pump pulse is followed by probing the induced optical property changes in the vicinity of the frequency threshold for the d band to Fermi surface transitions. This is shown to take place with a characteristic time constant of 350 fs, significantly shorter than previously reported in gold. This difference is ascribed to a weaker screening of the electron-electron interaction by the d-band electrons in silver than in gold. These results are in quantitative agreement with numerical simulations of the electron relaxation dynamics using a reduced static screening of the electron-electron Coulomb interaction, and including bound electron screening. Electron-lattice thermalization has been studied using a probe frequency out of resonance with the interband transitions. In both materials, the transient nonthermal nature of the electron distribution leads to the observation of a short-time delay reduction of the energy-loss rate of the electron gas to the lattice, in very good agreement with our theoretical model.