Electron-ion coincidence study of photofragmentation of the CdCl(2) molecule

In this work, the photofragmentation subsequent to valence and Cd4d photoionization 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 , Cd⁺ and CdCl⁺. The Cd4d^{? 1} states 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 initio calculations, and the calculated energies were found to agree with the detected fragment appearances. Copyright © 2011 John Wiley & Sons, Ltd.