Sub-100-fs energy transfer in coenzyme NADH is a coherent process assisted by a charge-transfer state.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
08 Jun 2024
08 Jun 2024
Historique:
received:
18
09
2023
accepted:
15
05
2024
medline:
9
6
2024
pubmed:
9
6
2024
entrez:
8
6
2024
Statut:
epublish
Résumé
Excitation energy transfer (EET) is a key photoinduced process in biological chromophoric assemblies. Here we investigate the factors which can drive EET into efficient ultrafast sub-ps regimes. We demonstrate how a coherent transport of electronic population could facilitate this in water solvated NADH coenzyme and uncover the role of an intermediate dark charge-transfer state. High temporal resolution ultrafast optical spectroscopy gives a 54±11 fs time constant for the EET process. Nonadiabatic quantum dynamical simulations computed through the time-evolution of multidimensional wavepackets suggest that the population transfer is mediated by photoexcited molecular vibrations due to strong coupling between the electronic states. The polar aqueous solvent environment leads to the active participation of a dark charge transfer state, accelerating the vibronically coherent EET process in favorably stacked conformers and solvent cavities. Our work demonstrates how the interplay of structural and environmental factors leads to diverse pathways for the EET process in flexible heterodimers and provides general insights relevant for coherent EET processes in stacked multichromophoric aggregates like DNA strands.
Identifiants
pubmed: 38851775
doi: 10.1038/s41467-024-48871-4
pii: 10.1038/s41467-024-48871-4
doi:
Substances chimiques
NAD
0U46U6E8UK
Water
059QF0KO0R
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
4900Subventions
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0022225
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0022225
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0022225
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0022225
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0022225
Informations de copyright
© 2024. The Author(s).
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