Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

The UV Photoinduced Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast Electron Diffraction

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [4];  [4];  [4];  [3];  [4];  [4];  [1];  [4];  [4];  [5];  [4];  [1];  [4];  [4];  [6];  [4];  [1] more »;  [7];  [5];  [4];  [8];  [4];  [5];  [5];  [1];  [5];  [4];  [9];  [4];  [3];  [4];  [1];  [4];  [9];  [9];  [1];  [2];  [1] « less
  1. University of Nebraska-Lincoln, NE (United States)
  2. University of Oxford (United Kingdom)
  3. Brown University, Providence, RI (United States)
  4. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  5. Kansas State University, Manhattan, KS (United States)
  6. Louisiana State University, Baton Rouge, LA (United States)
  7. Diamond Light Source Ltd, Didcot (United Kingdom)
  8. Extreme Light Infrastructure (ERIC), Dolni Brezany (Czechia)
  9. Tsinghua University, Beijing (China)
+ Show Author Affiliations
Conjugated cyclic organic molecules are common across many fields such as pharmaceuticals, are naturally occurring in biological systems, and are used in synthetic materials. One particular area of interest from a photochemical point of view is the formation of highly strained cyclic organics. We investigate the photoinduced reaction of cyclopentadiene, a five-membered organic ring molecule which can form strained three and four carbon rings after photoexcitation with UV light, with the gas-phase ultrafast electron diffraction instrument at the SLAC MeV-UED facility. Electron diffraction offers a direct probe sensitive to the nuclear geometry during the reaction, allowing for the determination of the distribution of products formed following photoexcitation. We observe the simultaneous formation of the highly strained ring- closed bicyclo[2.1.0]pentene and vibrationally hot cyclopentadiene within the temporal resolution of the experiment, and determine the relative yield of all reaction products. Furthermore, the experimental results are in good agreement with the predictions of trajectory simulations.
Research Organization:
University of Nebraska-Lincoln, NE (United States)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); Leverhulme Trust; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-76SF00515; FG02-86ER13491; SC0017995; SC0020276
OSTI ID:
3003777
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 48 Vol. 129; ISSN 1089-5639; ISSN 1520-5215
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (31)

Strain Release Chemistry of Photogenerated Small‐Ring Intermediates journal January 2021
The Norbornadiene/Quadricyclane Pair as Molecular Solar Thermal Energy Storage System: Surface Science Investigations journal March 2024
MCSCF study of the thermal isomerization of tricyclo[2.1.0.02,5]pentane to 1,3‐cyclopentadiene journal December 2003
Newton-X: a surface-hopping program for nonadiabatic molecular dynamics: Newton-X
  • Barbatti, Mario; Ruckenbauer, Matthias; Plasser, Felix
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1158
journal June 2013
BAGEL: Brilliantly Advanced General Electronic-structure Library: BAGEL journal August 2017
Nonadiabatic dynamics: The SHARC approach
  • Mai, Sebastian; Marquetand, Philipp; González, Leticia
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6 https://doi.org/10.1002/wcms.1370
journal May 2018
Ultrafast electron diffraction: structures in dissociation dynamics of Fe(CO)5 journal December 1997
Ultrafast photochemistry of cyclopentadiene: Competing hydrogen migration and electrocyclic ring closure journal September 2005
Rings in Clinical Trials and Drugs: Present and Future journal June 2022
The Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast X-ray Scattering journal May 2024
Designing Efficient Solar-Thermal Fuels with [n.n](9,10)Anthracene Cyclophanes: A Theoretical Perspective journal January 2018
SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings journal March 2011
Phototransposition of carbon atoms in cyclopentadiene. Photoisomerization of cyclopentadiene to tricyclo[2.1.0.02,5]pentane journal June 1977
Photolysis of cyclopentadienide and cyclopentadiene journal November 1971
Bicyclo[2.1.0]pent-2-ene journal February 1966
Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction journal February 2024
Isomerizations of Bicyclo[2.1.0]pent-2-ene and Tricyclo[2.1.0.0 2,5 ]pentane into Cyclopenta-1,3-diene:  A Computational Study by DFT and High-Level ab Initio Methods journal January 2004
Super-resolution femtosecond electron diffraction reveals electronic and nuclear dynamics at conical intersections journal July 2025
The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction journal April 2019
Femtosecond gas phase electron diffraction with MeV electrons journal January 2016
Mapping the photochemistry of cyclopentadiene: from theory to ultrafast X-ray scattering journal January 2023
Photo-induced structural dynamics of o-nitrophenol by ultrafast electron diffraction journal January 2024
Ultrafast structural dynamics of UV photoexcited cis,cis-1,3-cyclooctadiene observed with time-resolved electron diffraction journal January 2025
Between ethylene and polyenes - the non-adiabatic dynamics of cis-dienes journal January 2012
Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients journal August 2011
Valence transitions in 1,3‐cyclopentadiene, 1,3‐cyclohexadiene, and 1,3‐cycloheptadiene journal September 1985
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory journal July 2015
Femtosecond gas-phase mega-electron-volt ultrafast electron diffraction journal September 2019
Simultaneous observation of nuclear and electronic dynamics by ultrafast electron diffraction journal May 2020
Conformer-specific photochemistry imaged in real space and time journal October 2021

Similar Records

Related Subjects

Computational Chemistry
Electron Diffraction
Mathematical Methods
Molecules
Reaction Products