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The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction.
Wolf, T J A; Sanchez, D M; Yang, J; Parrish, R M; Nunes, J P F; Centurion, M; Coffee, R; Cryan, J P; Gühr, M; Hegazy, K; Kirrander, A; Li, R K; Ruddock, J; Shen, X; Vecchione, T; Weathersby, S P; Weber, P M; Wilkin, K; Yong, H; Zheng, Q; Wang, X J; Minitti, M P; Martínez, T J.
Afiliação
  • Wolf TJA; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. thomas.wolf@stanford.edu.
  • Sanchez DM; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Yang J; Department of Chemistry, Stanford University, Stanford, CA, USA.
  • Parrish RM; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Nunes JPF; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Centurion M; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Coffee R; Department of Chemistry, Stanford University, Stanford, CA, USA.
  • Cryan JP; Department of Chemistry, University of York, York, UK.
  • Gühr M; Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, NE, USA.
  • Hegazy K; Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, NE, USA.
  • Kirrander A; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Li RK; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Ruddock J; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Shen X; Institut für Physik und Astronomie, Universität Potsdam, Potsdam, Germany.
  • Vecchione T; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Weathersby SP; Department of Physics, Stanford University, Stanford, CA, USA.
  • Weber PM; EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, UK.
  • Wilkin K; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Yong H; Department of Chemistry, Brown University, Providence, RI, USA.
  • Zheng Q; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Wang XJ; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Minitti MP; SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Martínez TJ; Department of Chemistry, Brown University, Providence, RI, USA.
Nat Chem ; 11(6): 504-509, 2019 06.
Article em En | MEDLINE | ID: mdl-30988415
ABSTRACT
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 subångström 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.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article