Direct observation of the rate for cis.RAR.trans and trans.RAR.cis photoisomerization of stilbene with picosecond laser photolysis.
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The rates for direct cis→trans and trans→cis photoisomerizations of stilbene in solution were measured with a newly developed monitor light source for picosecond laser photolysis in the UV region. The rate constant of the trans→cis isomerization is 1.2×10<SUP>10</SUP> s<SUP>−1</SUP> in hexane at 295 K. The fluorescence decay rate constant of the S<SUB>1</SUB> state of <I>trans</I>-stilbene has the same value. Thus, the decay of the S<SUB>1</SUB> state is the rate limiting step and the lifetime of an intermediate perpendicular state (<SUP>1</SUP>p) has to be very short. The cis→trans isomerization is very fast and the half life of the excited <I>cis</I>-isomer is less than a few picosecond. These observations strongly indicate that the isomerization reaction proceeds through the potential surface of the singlet excited states.
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