Femtosecond time-resolved photoionization and photoelectron spectroscopy studies of ultrafast internal conversion in 1,3,5-hexatriene

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Abstract
Ultrafast photodynamics in a 1,3,5‐hexatriene are studied using femtosecond time‐resolved photoionization and photoelectron spectroscopy. The trans and cis isomers have distinctly different dynamics following excitation at the S 2 origin near 250 nm. An intermediate, presumably the S 1 state, is observed for both trans and cis isomers with lifetimes of 270 fs and 730 fs, respectively. Time‐delayed photoelectron spectra of cis‐hexatriene determine a 300 fs time scale for vibrational energy redistribution within the intermediate S 1 state.