Theoretical study of excited electronic states at surfaces, link with photo-emission and photo-desorption experiments

Excited electronic states at surfaces play a very important role in a variety of surface processes. These excited states have a finite lifetime due to electron-transfer processes and their efficiency as reaction intermediates depends crucially on their lifetime. A review of several physical situations, where an excited electronic state localized on an atom interacting with a metal surface intervenes in a surface process, is presented with an emphasis on the way the metal electronic structure influences the excited state dynamics. Examples are chosen among the alkali/metal systems, stressing how the same transient electronic state can influence different dynamical processes.