Abstract

Dynamics of the self-trapped excitons (STE) in quasi-one-dimensional halogen-bridged mixed-valence platinum complexes [Pt(en) 2][Pt(en) 2X 2](ClO 4) 4 (en=ethylenediamine, X=Cl or Br) has been studied by luminescence up-conversion technique. Time evolution of the luminescence from STE has been studied from 0.79 to 2.1 eV in the X=Cl system with a time resolution of 180 fs. The cooling time of hot STEs was determined as 210 fs, and the formation time of STE was found to be shorter than 140 fs, which is limited by our time resolution. In the X=Br system, we achieved a time resolution of 90 fs and succeeded in observing the wave packet oscillation in the adiabatic potential well of STE by luminescence for the first time. The period of the local mode oscillation is 290 fs (97 cm −1) and the damping time constant is 430 fs. Usefulness of the up-conversion spectroscopy for wave packet observation is demonstrated.

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