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Ultrafast photoisomerization of pinacyanol : Watching an excited state reaction transiting from barrier to barrierless forms

Photoisomerization of 1,1′-diethyl-2,2′-carbocyanine iodide (pinacyanol) in alcohols was investigated by means of femtosecond time-resolved absorption spectroscopy. Only one out of two possible types of photoisomer was found. Viscosity-dependent kinetics indicate that the excited state dynamics consist of two parts, associated with a barrier-crossing observed in the blue side of stimulated emissio