The Vacuum UV photoabsorption spectroscopy of Vinyl Fluoride (C2H3F): The vibrational fine structure and its analysis.

[en] The vacuum UV photoabsorption spectrum of C2H3F has been examined in detail between 6 eV and 25 eV photon energy by using synchrotron radiation. The analysis of the data is supported by ab initio quantum mechanical calculations applied to valence and Rydberg excited states of C2H3F. At 7.6 eV the pi-pi* and the 2a"->3s transitions are observed. An analysis is proposed and applied to the mixed fine structure belonging to these transitions. For the pi->pi* transition one single long vibrational progression is observed with hcwe= 95±7 meV (766±56 cm-1) and its adiabatic excitation energy is 6.892 eV (55 588 cm-1). The 2a"->3s transition is characterized by a single short progression with hc e= 167±10 meV (1 350±80 cm-1)starting at 6.974 eV (56 249 cm-1). From the present ab initio calculations these two wavenumbers best correspond to the vibrational modes v9 (CH2 rock in-plane, FCCbend) and v6 (CH2 rock in-plane, CF stretch) calculated at 615 cm-1 in the pi* state and 1 315 cm-1 in the (2A")3s Rydberg state respectively. The C=C stretching could not be excluded. The dense structured spectrum observed between 8.0 eV and 10.5 eV has been analyzed in terms of vibronic transitions to Rydberg states all converging to the C2H3F+(X2A") ionic ground state. An analysis of the associated complex fine structure of the individual Rydberg states has been attempted providing average values of the wavenumbers, e.g., for the (2A")3p Rydberg state hcw9= 60±1 meV (or 484±8 cm-1), hcw7= 151±7 meV (or 1 218±60 cm-1), hcw4= 191±3 meV (or 1 540±24 cm-1). The assignment of hcw= 105±5 meV (or 823±40 cm-1) is discussed. These experimental values are in good agreement with the theoretical predictions for C2H3F+ [R. Locht, B. Leyh, D. Dehareng, K. Hottmann, H. Baumgärtel, Chem.Phys. (in press)]. Above 10.5 eV and up to 25 eV several broad and strong bands are tentatively assigned to transitions to valence (V-V) and/or Rydberg (V-R) states converging to excited ionic states of C2H3F.

Research Center/Unit :

Laboratoire de dynamique Moléculaire

Disciplines :

Chemistry

Author, co-author :

Locht, Robert ; Université de Liège - ULiège > Département de Chimie(Faculté des sciences) > Laboratoire de Dynamique Moléculaire (Sciences)

Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire

Dehareng, Dominique ; Université de Liège - ULiège > Centre d'ingénierie des protéines

Jochims, H.-W.; Freie Universität Berlin

Baumgärtel, H.; Freie Universität Berlin

Language :

English

Title :

The Vacuum UV photoabsorption spectroscopy of Vinyl Fluoride (C2H3F): The vibrational fine structure and its analysis.

Alternative titles :

[fr] La spectroscopie d'absorption sous vide du fluorure de Vinyl (C2H3F): la structure fine de vibration et son analyse.

Publication date :

25 August 2009

Journal title :

Chemical Physics

ISSN :

0301-0104

Publisher :

Elsevier Science, Amsterdam, Netherlands

Volume :

362

Issue :

Pages :

97-108

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

http://www.atmosphere.mpg.de/spectral-atlas-mainz

Funders :

Union Européenne = European Union - UE = EU (TMR and I3)

Commentary :

- PDF-version of Editor's Postprint available on request - Version-pdf du tiré-à-part disponible sur demande

Available on ORBi :

since 15 July 2009

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