Difluorocarbene studied with threshold photoelectron spectroscopy (TPES): Measurement of the first adiabatic ionization energy (AIE) of CF2

Fabrizio Innocenti, Marie Eypper, Edmond P.F. Lee, Stefano Stranges, Kam Wah Mok, Foo Tim Chau, George C. King, John M. Dyke

Research output: Journal article publicationJournal articleAcademic researchpeer-review

15 Citations (Scopus)

Abstract

The first photoelectron band of difluorocarbene CF2, has been studied by threshold photoelectron (TPE) spectroscopy. CF2was prepared by microwave discharge of a flowing mixture of hexafluoropropene, C3F6, and argon. A vibrationally resolved band was observed in which at least twenty-two components were observed. In the first PE band of CF2, the adiabatic ionization energy differs significantly from the vertical ionization energy because, for the ionization CF2+(X̃2A1)+e-← CF2(X̃1A1), there is an increase in the FCF bond angle (by ≈20°) and a decrease in the C-F bond length (by ≈ 0.7 Å). The adiabatic component was not observed in the experimental TPE spectrum. However, on comparing this spectrum with an ab initio/Franck-Condon simulation of this band, using results from high-level ab initio calculations, the structure associated with the vibrational components could be assigned. This led to alignment of the experimental TPE spectrum and the computed Franck-Condon envelope, and a determination of the first adiabatic ionization energy of CF2as (11.362± 0.005) eV. From the assignment of the vibrational structure, values were obtained for the harmonic and fundamental frequencies of the symmetric stretching mode (v1′) and symmetric bending mode (v2′) in CF2+(X̃2A1). KGaA.
Original languageEnglish
Pages (from-to)11452-11460
Number of pages9
JournalChemistry - A European Journal
Volume14
Issue number36
DOIs
Publication statusPublished - 19 Dec 2008

Keywords

  • Carbenes
  • Photoelectron spectroscopy
  • Reactive intermediates
  • Vibrational spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

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