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

Abstract

Abstract. 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.

Plasmonic hot carrier dynamics in solid-state and chemical systems for energy conversion

“…The most detailed experimental probes of such mechanisms are pumpprobe measurements, where two laser pulses with a variable delay are used to excite electronic transitions in a molecule and then probe the progress of the chemical reaction that ensues on femtosecond timescales. In the field of femtochemistry, such techniques have been invaluable for tracking reaction mechanisms or even for changing the branching ratios of different processes [104][105][106][107][108][109][110][111][112][113][114][115]. These techniques are now becoming useful to probe the highly non-equilibrium processes driven by plasmonic hot carriers [36,39,116].…”

Theoretical study of the ionization of an alkali atom adsorbed on a metal surface by a laser-assisted subfemtosecond pulse

“…Experience acquired in similar studies ͑see Ref. 21 and 22 and references therein͒ allows us to recommend the cylindrical coordinate system as more suitable for studying problems with adsorbates. However, one has to take into account the strong field of the nucleus in this coordinate system that causes a substantial technical problem.…”