Femtosecond laser studies of the cis-stilbene photoisomerization reactions

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Abstract
Femtosecond laser studies have been performed on the photoisomerization reactions of cis‐stilbene to obtain the most detailed understanding to date of a polyatomic isomerization reaction in a condensed phase environment. These experiments demonstrate that vibrationally hot product molecules are formed within a few hundred femtoseconds of the escape of the molecule from the cis* region of the potential energy surface. Although the cis to trans reaction may proceed via a twisted intermediate structure, this intermediate is not intercepted on the ∼150 fs time scale. The frictional effects on the cis to trans reaction coordinate are found to be important and account for the anisotropy of the trans product molecules. Specific experiments presented in detail are the absorption spectrum of electronically excited cis molecules (cis*); the anisotropy decays for cis* showing motion along the reaction coordinate; the detection of the trans‐stilbene product using transient fluorescence and transient absorption, confirming that the reaction generates hot product states and that the Franck–Condon modes are largely spectators in the reaction; the anisotropy (alignment) of trans product molecules illustrating the effect of friction coupling overall motion to the reaction coordinate; and a theoretical treatment of three‐pulse anisotropy experiments.