Nuclear dynamics and electronic structure of molecules by resonant Auger spectroscopy

Abstract

Resonant Auger spectroscopy is used to study the molecular core-excited states with an inner-shell electron promoted to the lowest unoccupied molecular orbital. Dissociating Cl2p→σ ∗ excitations are investigated in the HCl and Cl 2 molecules, where the resonant Auger electron spectra exhibit both molecular and atomic features, depending on the time scale of the dissociation. The use of electron time-of-flight analyzers in combination with two-dimensional (in electron and photon energies) mapping technique allows to create a detailed picture of the interplay between dissociation and Auger decay. Also a Renner–Teller-split bound excited state, C1s→π ∗ is studied in the CO 2 molecule. Here, the Auger spectra recorded with high-resolution SES-200 hemispherical analyzer exhibit strong photon energy dependency across the resonance. From the analysis and semi-empirical modelling, properties of the core-excited state are derived.