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Photochemical isomerization of cis-stilbene in Ar and Kr clusters is studied by selectively measuring the trans-stilbene product formation rate with less than 1-psec time resolution. The observed trans-stilbene rise times are biexponential: The fast component is 1.7 ± 0.4 psec in Ar and 3.0 ± 0.3 psec in Kr, and the slow component is 16 ± 1 psec independently of the rare-gas solvent. It is proposed that the biexponential rise time is due to different decay rates for the vibrationally hot and relaxed phantom intermediate state.
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Petek et al. (1990) studied this question.
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