A comprehensive picture of the ultrafast excited-state dynamics of retinal
Literature Information
Oliver Flender, Mirko Scholz, Jonas Hölzer, Kawon Oum, Thomas Lenzer
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 (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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