Fast electronic relaxation in metal nanoclusters via excitation of   coherent shape deformations: Circumventing a bottleneck
  Electron-phonon relaxation in size-quantized systems may become inhibited when the spacing of discrete electron energy levels exceeds the magnitude of the phonon frequency. We show, however, that nanoclusters can support a fast nonradiative relaxation channel which derives from their distinctive ability to undergo Jahn-Teller shape deformations. Such a deformation represents a collective and coherent vibrational excitation and enables electronic transitions to occur without a multiphonon bottleneck. We analyze this mechanism for a metal cluster within the analytical framework of a three-dimensional potential well undergoing a spheroidal distortion. An expression for the time evolution of the distortion parameter is derived, the electronic level crossing condition formulated, and the probability of electronic transition at a level crossing is evaluated. An application to electron-hole recombination in a closed-shell aluminum cluster with 40 electrons shows that the short (~250 fs) excitation lifetime observed in recent pump-probe experiments can be explained by the proposed mechanism. 
Vitaly V. Kresin and Yu. N. Ovchinnikov