Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/17642
Title: Difluorocarbene studied with threshold photoelectron spectroscopy (TPES) : measurement of the first adiabatic ionization energy (AIE) of CF2
Authors: Innocenti, F
Eypper, M
Lee, EPF
Stranges, S
Mok, DKW 
Chau, FT
King, GC
Dyke, JM
Keywords: Carbenes
Photoelectron spectroscopy
Reactive intermediates
Vibrational spectroscopy
Issue Date: 2008
Publisher: Wiley-Blackwell
Source: Chemistry - a European journal, 2008, v. 14, no. 36, p. 11452-11460 How to cite?
Journal: Chemistry - A European Journal 
Abstract: The first photoelectron band of difluorocarbene CF2, has been studied by threshold photoelectron (TPE) spectroscopy. CF2 was 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 CF 2 + (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 CF2 as (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).
URI: http://hdl.handle.net/10397/17642
DOI: 10.1002/chem.200801699
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