Transient hole‐burning and time‐resolved fluorescence spectra of dye molecules in solution: Evidence for ground‐state relaxation and hole‐filling effect

A picosecond transient hole‐burning (THB) spectroscopy has been performed for organic dyes in solution. The THB spectra of rhodamine 640 have been found to show a time‐dependent spectral change. This phenomenon corresponds to the solvent relaxation effect observed in the time‐resolved fluorescence (TRF) spectrum. Although TRF spectrum is related only to the excited‐state relaxation, THB spectrum is affected by both ground‐ and excited‐state relaxations. Comparing with the TRF spectrum measured under the same exciting energy, we have clarified the presence of the ground‐state relaxation. Further, the THB spectrum of styryl‐8 gives an antihole between well‐separated two holes corresponding to ground‐ and excited‐state contributions. This may originate from the hole‐filling effect due to the nonadiabatic relaxation from the nonequilibrium excited state to the ground state. The analysis based on a configuration coordinate model gives an overall understanding for these phenomena.

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