2024-03-28T22:33:39Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/459852021-10-27T07:22:37Zcom_10261_115com_10261_3col_10261_368
00925njm 22002777a 4500
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Goikoetxea, Itziar
author
Beltrán, Juan
author
Meyer, Jörg
author
Juaristi Oliden, Joseba Iñaki
author
Alducin Ochoa, Maite
author
Reuter, Karsten
author
2012-01
We study the gas-surface dynamics of O2 at Ag(111) with the particular objective to unravel whether electronic non-adiabatic effects are contributing to the experimentally established inertness of the surface with respect to oxygen uptake. We employ a first-principles divide and conquer approach based on an extensive density-functional theory mapping of the adiabatic potential energy surface (PES) along the six O2 molecular degrees of freedom. Neural networks are subsequently used to interpolate these grid data to a continuous representation. The low computational cost with which forces are available from this PES representation allows then for a sufficiently large number of molecular dynamics trajectories to quantitatively determine the very low initial dissociative sticking coefficient at this surface. Already these adiabatic calculations yield dissociation probabilities close to the scattered experimental data. Our analysis shows that this low reactivity is governed by large energy barriers in excess of 1.1 eV very close to the surface. Unfortunately, these adiabatic PES characteristics render the dissociative sticking a rather insensitive quantity with respect to a potential spin or charge non-adiabaticity in the O2–Ag(111) interaction. We correspondingly attribute the remaining deviations between the computed and measured dissociation probabilities primarily to unresolved experimental issues with respect to surface imperfections.
New Journal of Physics 14: 013050 (2012)
1367-2630
http://hdl.handle.net/10261/45985
10.1088/1367-2630/14/1/013050
http://dx.doi.org/10.13039/501100003339
http://dx.doi.org/10.13039/501100001659
http://dx.doi.org/10.13039/501100004837
Non-adiabatic effects during the dissociative adsorption of O2 at Ag(111)? A first-principles divide and conquer study