Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
18 May 2023
18 May 2023
Historique:
received:
27
10
2022
accepted:
28
04
2023
medline:
19
5
2023
pubmed:
19
5
2023
entrez:
18
5
2023
Statut:
epublish
Résumé
Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.
Identifiants
pubmed: 37202402
doi: 10.1038/s41467-023-38513-6
pii: 10.1038/s41467-023-38513-6
pmc: PMC10195774
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
2795Subventions
Organisme : DOE | LDRD | Lawrence Livermore National Laboratory (LLNL)
ID : DE-AC52-07NA27344
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-SC0014170
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-AC02-76SF00515
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-AC02-76SF00515
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-AC02-76SF00515
Organisme : DOE | SC | Basic Energy Sciences (BES)
ID : DE-AC02-76SF00515
Informations de copyright
© 2023. The Author(s).
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