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

Science  15 Mar 2013:
Vol. 339, Issue 6125, pp. 1302-1305
DOI: 10.1126/science.1231711

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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.

Abstract

We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells—chemisorbed and precursor state separated by an entropy barrier—explain the anomalously high prefactors often observed in desorption of molecules from metals.

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