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Valence shell electronically excited states of norbornadiene and quadricyclane

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0187707· OSTI ID:2396808
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [9];  [9];  [8];  [10];  [9];  [11];  [9];  [12];  [9];  [9];  [5];  [13] more »;  [12];  [14];  [15];  [9] « less
  1. Univ. of Oxford (United Kingdom); SLAC
  2. Science and Technology Facilities Council (STFC), Warrington (United Kingdom). Daresbury Lab.
  3. Univ. College London (United Kingdom)
  4. Consiglio Nazionale delle Ricerche (CNR), Milano (Italy). Istituto di Fotonica e Nanotecnologie (CNR-IFN); Politecnico di Milano (Italy)
  5. Consiglio Nazionale delle Ricerche (CNR), Milano (Italy). Istituto di Fotonica e Nanotecnologie (CNR-IFN)
  6. Synchrotron SOLEIL, Gif-sur-Yvette (France)
  7. Kansas State Univ., Manhattan, KS (United States); University of Oulu (Finland)
  8. Friedrich-Alexander University Erlangen-Nuremberg, Erlangen (Germany)
  9. Kansas State Univ., Manhattan, KS (United States)
  10. Univ. of Nebraska, Lincoln, NE (United States)
  11. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  12. Brown Univ., Providence, RI (United States)
  13. Univ. of Oxford (United Kingdom); Kansas State Univ., Manhattan, KS (United States)
  14. Univ. of Bristol (United Kingdom)
  15. Univ. of Oxford (United Kingdom)
+ Show Author Affiliations

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1–11A1 (3sa1 ← 5b1) band and that predicted by Franck–Condon and Herzberg–Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ~5.4 and 7.0 eV.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515; SC0020276; FG02-86ER13491; SC0017995
OSTI ID:
2396808
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 160; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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