The temporal evolution of the photoexcited state in quasi-one-dimensional (1D) halogen-bridged platinum complexes $\left[\mathrm{Pt}\right(\mathrm{en}{)}_2\left]\right[\mathrm{Pt}\left(\mathrm{en}{)}_2{X}_2\right]({\mathrm{ClO}}_4{)}_4$ (abbreviated as $\mathrm{Pt}-X,$ $X=\mathrm{C}\mathrm{l},$ Br or I), has been comprehensively studied by femtosecond time-resolved luminescence spectroscopy. In Pt-Cl, new short-lived hot luminescence is found in the low-energy side of a self-trapped exciton (STE) luminescence band. The overall behavior of the STE luminescence band within 2 ps is well explained by the vibrational relaxation of the STE. The behavior is reproduced by a model calculation based on wave packet propagation on an interaction mode composed of frequency-dispersed bulk phonons. This model is also applied to the previous results in Pt-Br. For both Pt-Cl and Pt-Br, the frequency spectra of phonons which compose the interaction mode have been estimated. In Pt-I, the STE luminescence decays much faster than those in Pt-Cl and Pt-Br, showing existence of more effective nonradiative decay channel.

• Received 18 March 2002

DOI:https://doi.org/10.1103/PhysRevB.66.155112