Dynamics of energy transport in ternary molecular solids. II. Time evolution of naphthalene fluorescence

The spectrally resolved time-evolution of free and trapped singlet excitons was obtained at liquid-helium temperature for ternary crystals of perdeuteronaphthalene/naphthalene/betamethylnaphthalene (host/guest/supertrap). The naphthalene guest (donor) concentration varied between 0.30 and 0.99 mole fraction, while the supertrap (acceptor) concentrations were 10-4-10-5. At the lower guest concentrations (0.50 and below) the naphthalene-exciton decay time approaches the natural lifetime ([approximate] 122 ns). At higher concentrations, the decay is much shorter and extremely non-exponential. This behavior is inconsistent with simple homogeneous kinetics schemes that use a time-independent rate constant for energy transport. Above the percolation concentration (0.60 naphthalene) we fitted the experimental results with a random-flight-kinetic model, incorporating correlated random walks on the percolating guest cluster. The best fit was obtained for a "coherence length" (mean free path) of [approximate] 102 lattice units. These results are in good agreement with previous steady-state studies on the same samples, and seem to indicate a partial coherence of the exciton transport in both pure and substitutionally disordered crystals at these low temperatures.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/25161/1/0000597.pd