In reviewing the photochemistry of polyenes (from dienes and trienes to the visual retinyl chromophore),we categorize condensed-phase photochemical reactivity of molecules into two groups:those from thermally equilibrated excited species and those from unequilibrated excited species.Classical theories on radiationless transitions are useful for rationalizing the reactivity of molecules belonging to the first set only.The second group includes many of the exciting ultrafast photochemical reactions reported recently for polyenes (including dienes and trienes),in some cases with rates faster than vibrational relaxation.Much of the excited singlet-state reactions of polyenes,including the Hula-twist mechanism of photoisomerization,have been integrated with concepts introduced in other ultrafast spectroscopic/photochemical studies.Taking into consideration the special environment of the retinyl chromophore in rhodopsin,we propose a new mechanism for the phototrigger that accounts for its unusually fast rate of isomerization.
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