Abstract
Parker and Hatchard1 have convincingly demonstrated that delayed fluorescence exhibited by dissolved aromatic hydrocarbons A originates in the interaction of two triplet states, and that at low light intensities the overall process 1, followed by 2, is controlled by the first-order process 3 which is almost entirely responsible for triplet state decay under these conditions. To account for the presence of the dimer band in the delayed fluorescence spectrum of pyrene2, these authors3 suggest that process 1 involves Colpa's doubly-excited state 1A2 ** and the excimer 1A2* as intermediates, that is: where the energy-dependent process 1c competes with excimer fluorescence, process (4). This mechanism accounts for the observation3 that the ratio of intensities ID/IM of dimer to monomer bands in the delayed spectrum approaches a limiting non-zero value at zero concentration of A at room temperature; moreover, it requires a negative temperature coefficient of ID/IM which is indeed observed above 0° C as shown in Fig. 1.
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References
Parker, C. A., and Hatchard, C. B., Proc. Chem. Soc., 147, 386 (1962); Proc. Roy. Soc., A, 269, 574 (1962).
Stevens, B., and Hutton, E., Nature, 186, 1045 (1960).
Parker, C. A., and Hatchard, C. G., Trans. Farad. Soc., 59, 284 (1963).
Muel, B., doctoral dissertation (Univ. Paris, 1962).
Nieman, G. C., and Robinson, G. W., J. Chem. Phys., 37, 2150 (1962).
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TANAKA, C., TANAKA, J., HUTTON, E. et al. Delayed Fluorescence Spectrum of Pyrene Solutions at Low Temperatures. Nature 198, 1192 (1963). https://doi.org/10.1038/1981192a0
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DOI: https://doi.org/10.1038/1981192a0
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