Conjugation Length Dependence of Internal Conversion in Carotenoids: Role of the Intermediate State

We report on a sub-20-fs transient absorption study of the S2(1(1)B(+)(u))-->S1(2(1)A(-)(g)) internal conversion in a series of carotenoids with a number of conjugated double bonds (N) ranging from 5 to 15. For the longer carotenoids (N>or=9), the measurements reveal the existence of an additional intermediate excited state lying between the optically allowed S2 state and the lower-lying forbidden S1 state. This state enables us to explain the nonmonotonic dependence of the S2-->S1 conversion rate on N and is expected to play an important role in photosynthetic light harvesting.