RT Journal Article
T1 Non-adiabatic effects during the dissociative adsorption of O_(2) at Ag(111)? A first-principles divide and conquer study
A1 Goikoetxea, Itziar
A1 Beltrán Fínez, Juan Ignacio
A1 Meyer, Jörg
A1 Juristi, Iñaki
A1 Aducin, Maite
A1 Reuter, Karsten
AB We study the gas-surface dynamics of O_(2) 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 O_(2) 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 O_(2)–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.
PB IOP Publishing
SN 1367-2630
YR 2012
FD 2012-01-24
LK https://hdl.handle.net/20.500.14352/44682
UL https://hdl.handle.net/20.500.14352/44682
LA eng
NO © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft. We thank Professor A Kleyn for useful and clarifying discussions on their molecular beam experiments. The work of IG has been supported by the Spanish Research Council (CFM-CSIC, grant numbers JAE-Pre 08 0045 and 2010ESTCSIC-02167). Funding from the Deutsche Forschungsgeinschaft (RE 1509/7-1) is gratefully acknowledged. MA and IJ also acknowledge the Spanish Ministerio de Ciencia e Innovación (grant no. FIS2010-19609-C02-02).
NO Ministerio de Ciencia e Innovación (MICINN)
NO Spanish Research Council (CFM-CSIC)
NO Deutsche Forschungsgeinschaft
DS Docta Complutense
RD 8 abr 2025