Bohinc, R. Žitnik, M. Bučar, K. Kavčič, Matjaz Journel, L. Guillemin, R. Marchenko, T. Simon, M. Cao, Wei 2013-10-03 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 application/pdf https://folia.unifr.ch/global/documents/303589 https://folia.unifr.ch/documents/303589/files/cao_dcu.pdf eng info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4822326 info:eu-repo/semantics/openAccess License undefined The Journal of Chemical Physics. - 2014, vol. 139, no. 13, p. 134302 info:eu-repo/classification/udc/53 Dissociation of chloromethanes upon resonant σ* excitation studied by x-ray scattering http://purl.org/coar/resource_type/c_6501