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Title: Dissociative adsorption of O2 on unreconstructed metal (100) surfaces: Pathways, energetics, and sticking kinetics

An accurate description of oxygen dissociation pathways and kinetics for various local adlayer environments is key for an understanding not just of the coverage dependence of oxygen sticking, but also of reactive steady states in oxidation reactions. Density functional theory analysis for M(100) surfaces with M=Pd, Rh, and Ni, where O prefers the fourfold hollow adsorption site, does not support the traditional Brundle-Behm-Barker picture of dissociative adsorption onto second-nearest-neighbor hollow sites with an additional blocking constraint. Rather adsorption via neighboring vicinal bridge sites dominates, although other pathways can be active. The same conclusion also applies for M=Pt and Ir, where oxygen prefers the bridge adsorption site. Statistical mechanical analysis is performed based on kinetic Monte Carlo simulation of a multisite lattice-gas model consistent with our revised picture of adsorption. This analysis determines the coverage and temperature dependence of sticking for a realistic treatment of the oxygen adlayer structure.
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  1. Ames Laboratory
Publication Date:
OSTI Identifier:
Report Number(s):
IS-J 8298
Journal ID: ISSN 1098-0121
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 89; Journal Issue: 20
American Physical Society (APS)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States