A study of vibrational selectivity of electronic autoionization processes in using two-dimensional photoelectron spectroscopy

Two-dimensional photoelectron spectroscopy has been used to investigate vibrational selectivity accompanying electronic autoionizing decays of Rydberg states between the and ionization thresholds in . Measurements of electron yield as a function of both electron and photon energy have been carried out using tuneable synchrotron radiation. This study, which is the most comprehensive to date, has enabled the vast majority of the accessible vibrational levels of the ion to be investigated. The experimental resolution was good enough to observe individual vibrational levels and complex vibrational selectivity was evident throughout the two-dimensional spectrum. A significant number of the features in the spectrum could be ascribed to vibrational progressions in the symmetric stretch mode.