Abstract

Time-resolved fluorescence spectra for C60 mols. embedded in Ne and Ar matrixes and C70 in Ne matrixes were recorded using a synchroscan streak camera. In the case of C60, the decay times of the S1 state are identical for all fluorescence bands confirming that it is a state of mixed T1g, T2g, and Gg characters. Its lifetime is detd. by the intersystem crossing rate to the triplet manifold which increases in going from Ar to Ne matrixes. This is attributed to a change of the dominant symmetry character of S1 in the 2 matrixes. A transient, short-lived (.apprx.170 ps in Ne, .apprx.70 ps in Ar), S3 fluorescence of dominant Gg symmetry is also obsd., which feeds the S2/S1 population (of dominant T2g and T1g symmetry). Using the Energy Gap Law, a change of the S3 S2/S1 decay rate from Ne to Ar matrixes is attributed to the different no. of phonons needed to bridge the gap between these states and/or to an environment-dependent change of the coupling matrix element. In C70, the fluorescence from both S1 and S2 are populated at the same rate despite the 165 cm-1 energy gap between them. This is explained in terms of an intersystem crossing from the triplet state manifold. Finally, S2 decays predominantly to S1, while the latter decays to the triplet states by reversible intersystem crossing. These conclusions are confirmed by a simple kinetic model. [on SciFinder (R)]

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