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In this work, the photofragmentation subsequent to valence and Cd4dphotoionization of cadmium dichloride (CdCl2) were studied using He I and synchrotron excitation. The measurements were performed with a photoelectron‐photoion coincidence (PEPICO) setup, and the connection between the singly ionized electronic states and cationic fragments was investigated. The valence‐ionized states were found to lead to CdCl2+, Cd+and CdCl+. The Cd4d− 1states were found to lead only to Cl+ions. The observed charge transfer effect between Cd and Cl was concluded to take place due to internal conversion or fluorescence decay to dissociating valence states either directly or through consecutive fragmentation. The fragmentation energetics were investigated with molecular ab initiocalculations, and the calculated energies were found to agree with the detected fragment appearances. Copyright © 2011 John Wiley & Sons, Ltd.

The Xe 3d?13/2,5/2? (4s, 4p)?14d?1Auger transitions have been studied with the aid of high-resolution experiments and calculations which account for the final ionic state configuration interaction. Auger transitions from two spin-orbit split initial states were separated by measuring the M4,5NN4,5Auger electron spectra with two photon energies: one below and one above the M4ionization threshold. Calculations were found to reproduce the partial Auger rates and structures in the experimental M4,5N1,2,3N4,5spectra very well, which allowed revised assignments of the main structures from the previous studies.

The photoelectron spectrum of krypton was recorded with various photon energies from 60 to 88 eV in the binding energy range of Kr 4s photoelectron line and valence satellite lines. Strong photon energy dependence was found in the experimental cross-sections of the satellite lines. The high experimental resolution of the measured spectra allowed us to really separate close lying states. This, together with the measurement of the angular anisotropy parameter ? at h? = 88 eV enabled us to verify the origin of the satellite lines, i.e. whether they are created by shake-up, conjugated shake-up, or by correlation of bound or continuum states during 4s or 4p photoionization.

Cascade Auger transitions following the Xe 4d ? 6p excitation have been studied both experimentally and theoretically. The low kinetic energy part from 2 to 30 eV of the resonance Auger spectra has been recorded with different photon bandwidths which have enabled us to separate most of the first and second step Auger transitions from each other. The results for ion production obtained from the electron spectra are compared with the results of the partial ion yield spectra. The present theoretical results based on multiconfiguration Dirac-Fock (MCDF) approach are compared with the experimental findings and with earlier theoretical results. The discrepancies between the electron and ion data reported previously were found to originate from the difficulties in the treatment of the Auger group rates.

The partial ion yield spectra of Xeⁿ⁺ ions (n = 1–8) were detected by an ion time-of-flight mass analyser in the photon energy range of 664–694 eV, and the branching ratios of ions following the 3d⁻¹_5/2 ionization and the 3d_5/2→ 6p resonance excitation were obtained. The branching ratios were found to be almost the same. Theoretical de-excitation pathways and branching ratios of ions following the 3d_5/2→ 6p resonance excitation were obtained using the single-configuration approximation and a semi-empirical model, and results were compared with the experiments and the previously published calculations for the 3d⁻¹ ionization.

The partial ion yield spectra of Xen+ions (n= 1-8) were detected by an ion time-of-flight mass analyser in the photon energy range of 664-694 eV, and the branching ratios of ions following the 3d?15/2ionization and the 3d5/2? 6p resonance excitation were obtained. The branching ratios were found to be almost the same. Theoretical de-excitation pathways and branching ratios of ions following the 3d5/2? 6p resonance excitation were obtained using the single-configuration approximation and a semi-empirical model, and results were compared with the experiments and the previously published calculations for the 3d?1ionization.