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Results of optical studies of a new single-molecule system, terrylene molecules in a 2,3-dichloronaphthalene crystal, are presented for the first time. Analysis of the second-order fluorescence intensity correlation function shows that the external heavy-atom effect (due to the chlorine atoms) contributes to the increase of the intersystem crossing rate constant for the S1 → T1 transition, by one order of magnitude, whereas the rate constant for the T1 → S0 transition is only weakly influenced. [ABSTRACT FROM AUTHOR]