期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 8, 期 18, 页码 4407-4412出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.7b01780
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资金
- European Research Council Advanced Grant STRATUS ERC-AdG [291198]
- French Agence National de la Recherche [FEMTO-2DNA, ANR-1S-CE29-0010]
- LABEX iMUST of Lyon University, as part of the Investissements d'Avenir program of the French National Research Agency (ANR) [ANR-10-LABX-0064, ANR-11-IDEX-0007]
Single methylation at position C-10 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 S-1 and covalent S-2 states, reducing the excited-state lifetime by favoring the formation of a S-1 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 SI state as well as the interaction with the covalent S-2 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.
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