Thomas J. A. Wolf, David M. Sanchez, J. Yang, R. M. Parrish, J. P. F. Nunes, M. Centurion, R. Coffee, J. P. Cryan, Markus Gühr, Kareem Hegazy, Adam Kirrander, R. K. Li, J. Ruddock, Xiaozhe Shen, T. Vecchione, S. P. Weathersby, Peter M. Weber, K. Wilkin, Haiwang Yong, Q. Zheng, X. J. Wang, Michael P. Minitti, Todd J. Martinez
- The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms intoThe ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.…
MetadatenAuthor details: | Thomas J. A. WolfORCiD, David M. SanchezORCiD, J. Yang, R. M. Parrish, J. P. F. Nunes, M. Centurion, R. Coffee, J. P. Cryan, Markus GührORCiDGND, Kareem HegazyORCiD, Adam KirranderORCiD, R. K. Li, J. Ruddock, Xiaozhe ShenORCiD, T. Vecchione, S. P. Weathersby, Peter M. WeberORCiD, K. Wilkin, Haiwang YongORCiD, Q. Zheng, X. J. Wang, Michael P. MinittiORCiD, Todd J. MartinezORCiD |
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DOI: | https://doi.org/10.1038/s41557-019-0252-7 |
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ISSN: | 1755-4330 |
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ISSN: | 1755-4349 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/30988415 |
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Title of parent work (English): | Nature chemistry |
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Publisher: | Nature Publ. Group |
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Place of publishing: | London |
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Publication type: | Article |
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Language: | English |
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Date of first publication: | 2019/04/15 |
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Publication year: | 2019 |
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Release date: | 2021/02/02 |
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Tag: | Organic chemistry; Photochemistry; Physical chemistry; Theoretical chemistry |
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Volume: | 11 |
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Issue: | 6 |
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Number of pages: | 6 |
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First page: | 504 |
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Last Page: | 509 |
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Funding institution: | US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences DivisionUnited States Department of Energy (DOE); DOE BES SUF Division Accelerator & Detector RD program; Linac Coherent Light Source (LCLS) Facility; SLACStanford UniversityUnited States Department of Energy (DOE) [DE-AC02-05-CH11231, DE-AC02-76SF00515]; Lichtenberg Professorship of the Volkswagen Foundation; NSFNational Science Foundation (NSF); Wild Overseas Scholars Fund of the Department of Chemistry, University of York; US Department of Energy Office of Science, Basic Energy SciencesUnited States Department of Energy (DOE) [DE-SC0014170]; US Department of Energy, Office of Science, Basic Energy SciencesUnited States Department of Energy (DOE) [DE-SC0017995]; Carnegie Trust for the Universities of Scotland [CRG050414]; RSE/Scottish Government Sabbatical Research Grant [58507] |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
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DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
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Peer review: | Referiert |
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Publishing method: | Open Access / Green Open-Access |
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