A comprehensive picture of the ultrafast excited-state dynamics of retinal

Literature Information

Publication Date 2016-05-18
DOI 10.1039/C6CP01335J
Impact Factor 3.676
Authors

Oliver Flender, Mirko Scholz, Jonas Hölzer, Kawon Oum, Thomas Lenzer


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Abstract

All-trans retinal is the chromophore of microbial rhodopsins initiating energy conversion and cellular signalling by subpicosecond photoinduced switching. Here, we provide detailed UV-Vis transient absorption experiments to disentangle the complex photochemistry of this polyene, which is governed by its terminal aldehyde group. After photoexcitation to the S2(1Bu+) state, the system exhibits polarity-dependent branching, populating separate S1(1Ag−) and intramolecular charge transfer (ICT) species. In all solvents, population of a singlet nπ* state from S1 is observed which represents the precursor of the T1 triplet state. While triplet formation dominates in nonpolar solvents (67% quantum yield), it is dramatically reduced in polar solvents (4%). The channel closes completely upon replacing the aldehyde by a carboxyl group, due to an energetic up-shift of 1nπ*. In that case, internal conversion via the ICT species becomes the main pathway, with preferential formation of the initially excited isomer.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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