Journal article

Dissociation of chloromethanes upon resonant σ* excitation studied by x-ray scattering

  • Bohinc, R. Jožef Stefan Institute, Ljubljana, Slovenia
  • Žitnik, M. Jožef Stefan Institute, Ljubljana, Slovenia - Faculty of Mathematics and Physics, University of Ljubljana, Slovenia
  • Bučar, K. Jožef Stefan Institute, Ljubljana, Slovenia
  • Kavčič, Matjaz Jožef Stefan Institute, Ljubljana, Slovenia
  • Journel, L. UPMC, Université Paris, France
  • Guillemin, R. UPMC, Université Paris, France
  • Marchenko, T. UPMC, Université Paris, France
  • Simon, M. UPMC, Université Paris, France
  • Cao, Wei Department of Physics, University of Oulu, Finland - Department of Physics, University of Fribourg, Switzerland
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  • The Journal of Chemical Physics. - 2014, vol. 139, no. 13, p. 134302
English The dissociation process following the Cl K-shell excitation to σ* resonances is studied by high resolution spectroscopy of resonant elastic and inelastic x-ray scattering on CH3Cl, CH2Cl2, CHCl3, and CCl4 molecules. Calculations employing the transition potential and Delta-Kohn-Sham DFT approach are in good agreement with the measured total fluorescence yield and show the presence of a second quasidegenerate group of states with σ* character above the lowest σ* unoccupied molecular orbital for molecules with more than one Cl atom. A bandwidth narrowing and a nonlinear dispersion behavior is extracted from the Kα spectral maps for both σ* resonances. The fitted data indicate that the widths of the Franck-Condon distributions for the first and second σ* resonances are comparable for all the molecules under study. In addition, an asymmetric broadening of the emission peaks is observed for resonant elastic x-ray scattering with zero detuning on both σ* resonances. This is attributed to the fast dissociation, transferring about 0.15 of the scattering probability into higher vibrational modes
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