Picosecond study of an intermediate in the trans to cis isomerization pathway of stiff stilbene

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Abstract
A picosecond spectroscopic study of trans 1,1′‐biindanylidene (‘‘stiff’’ stilbene) has exposed a transient absorption at 351 nm which is not an electronically excited state of the trans or cis forms. The signal strength increases with decreasing viscosity in a manner that is consistent with the decay of the excited trans molecules being the precursor of the new transient. The data suggest that after the viscosity dependent formation of the intermediate, it decays with a time constant of 10±3 ps into cis stiff stilbene. It is suggested that the intermediate is the ‘‘phantom’’ state of stilbene photochemistry.