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We study the role of collective surface excitations in the electronrelaxation in small metal particles. We show that the dynamically screenedelectron-electron interaction in a nanoparticle contains a size-dependentcorrection induced by the surface. This leads to new channels of quasiparticlescattering accompanied by the emission of surface collective excitations. Wecalculate the energy and temperature dependence of the corresponding rates,which depend strongly on the nanoparticle size. We show that thesurface-plasmon-mediated scattering rate of a conduction electron increaseswith energy, in contrast to that mediated by a bulk plasmon. In noble-metalparticles, we find that the dipole collective excitations (surface plasmons)mediate a resonant scattering of d-holes to the conduction band. We study therole of the latter effect in the ultrafast optical dynamics of smallnanoparticles and show that, with decreasing nanoparticle size, it leads to adrastic change in the differential absorption lineshape and a strong frequencydependence of the relaxation near the surface plasmon resonance. Theexperimental implications of our results in ultrafast pump-probe spectroscopyare also discussed.Comment: 29 pages including 6 figure

Size-dependent correlation effects in the ultrafast optical dynamics of metal nanoparticles