Lifetime broadening of atomic lines produced upon ultrafast dissociation of HCl and HBr

Ultrafast dissociation of the HCl and HBr molecules excited respectively to the 2p3/2 → σ* and 3d5/2 → σ* resonances are studied with high resolution photoelectron spectroscopy. Sharp vibrational molecular lines and broad atomic lines are observed. The analysis of the profile of the atomic lines gives access to the lifetimes of the inner shell 2p3/2 hole in the Cl* (2p3/2)−1 3s23p6 configuration, and the inner shell 3d5/2 hole in the Br* (3d5/2)−1 4s24p6 configuration.