Abstract
AbstractThe photoisomerization of trans‐stilbene after picosecond excitation at 308 nm has been studied by picosecond absorption at 500 or 616 nm in ethane and propane. Experiments were performed in gaseous ethane (30–54 bar), liquid ethane (42–6000 bar), and liquid propane (9–4050 bar). The pressure dependence of the reaction is modelled from isolated molecule conditions in low pressure gases up to diffusion control in high pressure liquids. In dense media marked solvent shifts of the reaction threshold energy are postulated which can be described by simple cluster — and cage — solvent shift models. UV spectra show similar solvent shifts as isomerization rates.
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