Real-Time Observation of Surface Bond Breaking with an X-ray Laser

Surface Molecules Not Quite Desorbing The dynamics of molecules desorbing from or adsorbing on surfaces requires that molecules rapidly gain or lose a large amount or translational and rotational energy to enter or leave the gas phase. An intermediate precursor state has long been invoked in which molecules interact weakly with the surface but translate along it and exchange energy without forming localized surface bonds. Dell'Angela et al. (p. 1302) found evidence for such a state in changes in x-ray absorption and emission spectra of CO molecules adsorbed on a ruthenium surface after optical excitation rapidly heated the surface. The use of a free electron laser provided high time resolution for x-ray spectroscopy studies. Density function theory and modeling of high temperature states revealed a state that forms from molecules that have not overcome the desorption barrier during heating and that are bonded less strongly than the chemisorbed state.