Abstract
We compare the adequacy of empirical frictional-coupling models to simulate the femtosecond-laser-induced desorption of molecular oxygen from Pd(1 1 1). We find that a model that incorporates temperature-dependent frictional coupling provides a superior description of the experimental observations compared to those incorporating temperature-independent frictional coupling. The implication is that the electron-mediated substrate-adsorbate coupling strength is dependent on the temperature of the substrate electronic distribution. There have been theoretical predictions of temperature-dependent coupling [M. Brandbyge, P. Hedegård, T.F. Heinz, J.A. Misewich, D.M. Newns, Phys. Rev. B 52 (1995) 6042; J.C. Tully, M. Gomez, M. Head-Gordon, J. Vac. Sci. Technol. A 11 (1993) 1914], and dependence of the efficiency of surface-molecule energy transfer on the electronic temperature is consistent with a resonance-enhanced process believed to be responsible for the photoinduced desorption in this and related systems. The model we describe also provides a simple explanation for the biexponential decay observed in the time-resolved correlation experiments.
Original language | English |
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Pages (from-to) | 3335-3349 |
Number of pages | 15 |
Journal | Surface Science |
Volume | 601 |
Issue number | 16 |
DOIs | |
Publication status | Published - Aug 15 2007 |
Keywords
- Computer simulations
- Desorption induced by electronic transitions
- Desorption induced by photon stimulation
- Dynamics
- Models of surface chemical reactions
- Oxygen
- Palladium
- Solid-gas interfaces
ASJC Scopus subject areas
- Condensed Matter Physics
- Surfaces and Interfaces
- Surfaces, Coatings and Films
- Materials Chemistry