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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03.10.2013
Published in:
- 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
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Physique
- Language
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- English
- Classification
- Physics
- License
- License undefined
- Identifiers
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- RERO DOC 209562
- DOI 10.1063/1.4822326
- Persistent URL
- https://folia.unifr.ch/unifr/documents/303589
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