Subpicosecond time resolved multiphoton ionization is demonstrated to be a useful technique for probing unimolecular dynamics in vapor phase samples. Vapor phase cis-stilbene molecules are observed to decay out of their initially prepared S1 state with a single exponential time constant of 0.32 ps. This decay, thought to correspond to a rapid twisting of the molecule about the ethylenic double bond, occurs in roughly one c=c double bond torsional vibrational period.
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Greene et al. (1983) studied this question.
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