5 years ago

Fine Tuning of Retinal Photoinduced Decay in Solution

Fine Tuning of Retinal Photoinduced Decay in Solution
Ivan Rivalta, Baptiste Demoulin, Marco Garavelli, Salvatore Flavio Altavilla
Single methylation at position C10 of the all-trans retinal protonated Schiff base switches its excited-state decay in methanol from a slower picosecond into an ultrafast, protein-like subpicosecond process. QM/MM modeling in conjunction with on-the-fly excited-state dynamics provides fundamental understanding of the fine-tuning mechanics that “catalyzes” the photoinduced decay of solvated retinals. Methylation alters the interplay between the ionic S1 and covalent S2 states, reducing the excited-state lifetime by favoring the formation of a S1 transient fluorescent state with fully inverted bond lengths that accounts for the recorded transient spectroscopy and from which a space-saving conical intersection seam is quickly (<1 ps) reached. Minimal and apparently innocent chemical modifications thus affect the characteristic intramolecular charge-transfer of the S1 state as well as the interaction with the covalent S2 excited state, eventually providing the high tunability of retinal photophysics and photochemistry and delivering a new concept for the rational design of retinal-based photoactive molecular devices.

Publisher URL: http://dx.doi.org/10.1021/acs.jpclett.7b01780

DOI: 10.1021/acs.jpclett.7b01780

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