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RADIATIVE AND NON‐RADIATIVE LOSSES IN THE RETINOL POLYENES

Abstract— The radiative fluorescence lifetimes of the all‐trans, 9 cis and 13 cis retinol, have been measured at various temperatures, and in various solvents. The comparison of these results and of the data calculated from the absorption spectra using the Strickler and Berg equation shows that the transition probabilities are at least one hundred times lower for the radiative emission than for the absorption. Such a discrepancy, which is a general property of the polyenic structure, is closely related to the magnitude of the shift between absorption and fluorescence spectra. We interpret the observed elongation of the radiative fluorescence lifetimes and the temperature dependence of the radiative transitions in the case of all trans retinol as being due to the fact that only the lowest vibrorotational sublevels of 1S1, have a reasonable radiative transition probability: the temperature dependence of the radiationless transitions is considered to be due to the existence of a non radiative decay pathway at 550cal/mole above the ‘0’ level.