The Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast X-ray Scattering.

Autor: Huang L; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Bertram L; Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom., Ma L; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Goff N; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Crane SW; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Odate A; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Northey T; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Carrascosa AM; Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom., Simmermacher M; Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom., Muvva SB; Department of Physics and Astronomy, University of Nebraska - Lincoln, Lincoln, Nebraska 68588, United States., Geiser JD; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Lueckheide MJ; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States., Phelps Z; Department of Physics, Kansas State University, Manhattan, Kansas 66506, United States., Liang M; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Cheng X; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Forbes R; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Robinson JS; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Hayes MJ; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Allum F; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Green AE; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.; European XFEL, Schenefeld 22869, Germany., Lopata K; Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, United States., Rudenko A; Department of Physics, Kansas State University, Manhattan, Kansas 66506, United States., Wolf TJA; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Centurion M; Department of Physics and Astronomy, University of Nebraska - Lincoln, Lincoln, Nebraska 68588, United States., Rolles D; Department of Physics, Kansas State University, Manhattan, Kansas 66506, United States., Minitti MP; SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States., Kirrander A; Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom., Weber PM; Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. A [J Phys Chem A] 2024 Jun 27; Vol. 128 (25), pp. 4992-4998. Date of Electronic Publication: 2024 May 06.
DOI: 10.1021/acs.jpca.4c02509
Abstrakt: The dynamics of cyclopentadiene (CP) following optical excitation at 243 nm was investigated by time-resolved pump-probe X-ray scattering using 16.2 keV X-rays at the Linac Coherent Light Source (LCLS). We present the first ultrafast structural evidence that the reaction leads directly to the formation of bicyclo[2.1.0]pentene (BP), a strained molecule with three- and four-membered rings. The bicyclic compound decays via a thermal backreaction to the vibrationally hot CP with a time constant of 21 ± 3 ps. A minor channel leads to ring-opened structures on a subpicosecond time scale.
Databáze: MEDLINE