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 |
|---|---|
| Pages (from-to) | 3335-3349 |
| Number of pages | 15 |
| Journal | Surface Science |
| Volume | 601 |
| Issue number | 16 |
| DOIs | |
| Publication status | Published - Aug 15 2007 |
Fingerprint
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
- Physical and Theoretical Chemistry
- Condensed Matter Physics
- Surfaces and Interfaces
Cite this
Temperature-dependent electron-mediated coupling in subpicosecond photoinduced desorption. / Szymanski, P.; Harris, Alex; Camillone, N.
In: Surface Science, Vol. 601, No. 16, 15.08.2007, p. 3335-3349.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Temperature-dependent electron-mediated coupling in subpicosecond photoinduced desorption
AU - Szymanski, P.
AU - Harris, Alex
AU - Camillone, N.
PY - 2007/8/15
Y1 - 2007/8/15
N2 - 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.
AB - 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.
KW - Computer simulations
KW - Desorption induced by electronic transitions
KW - Desorption induced by photon stimulation
KW - Dynamics
KW - Models of surface chemical reactions
KW - Oxygen
KW - Palladium
KW - Solid-gas interfaces
UR - http://www.scopus.com/inward/record.url?scp=34547677703&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34547677703&partnerID=8YFLogxK
U2 - 10.1016/j.susc.2007.06.004
DO - 10.1016/j.susc.2007.06.004
M3 - Article
VL - 601
SP - 3335
EP - 3349
JO - Surface Science
JF - Surface Science
SN - 0039-6028
IS - 16
ER -