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Gas phase thermal isomerization rates of trans-stilbene at 300 K obey theArrhenius law. In solution the rates increase ten-fold and depend only veryweakly on excitation wavelength or intramolecular temperature. Bothobservations are difficult to reconcile within RRKM theory. Previouslydiscussed mechanisms, like restricted IVR, nonadiabaticity, solvent-dependentbarriers, or excitation-induced cooling, may explain the increase of the ratesin solution but not their dependence on the excitation wavelength. The lattersuggests that solvent collisions can directly promote the isomerization.

Is photoisomerization of stilbene in solution directly promoted by solvent collisions?