The coverage dependence of oxygen adsorption energies on the fcc(111) surfaces of seven different transition metals (Rh, Ir, Pd, Pt, Cu, Au, and Ag) is demonstrated through density functional theory calculations on 20 configurations ranging from one to five adsorption sites and coverages up to 1 ML. Atom projected densities of states are used to demonstrate that the d-band mediated adsorption mechanism is responsible for the coverage dependence of the adsorption energies. This common bonding mechanism results in a linear correlation that relates the adsorption energies of each adsorbate configuration across different metal surfaces to each other. The slope of this correlation is shown to be related to the characteristics of the valence d-orbitals and band structure of the surface metal atoms. Additionally, it is shown that geometric similarity of the configurations is essential to observe the configurational correlations.
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14 March 2011
Research Article|
March 14 2011
Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces
Spencer D. Miller;
Spencer D. Miller
Department of Chemical Engineering,
Carnegie Mellon University
, Pittsburgh, Pennsylvania 15213, USA
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Nilay İnoğlu;
Nilay İnoğlu
Department of Chemical Engineering,
Carnegie Mellon University
, Pittsburgh, Pennsylvania 15213, USA
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John R. Kitchin
John R. Kitchin
a)
Department of Chemical Engineering,
Carnegie Mellon University
, Pittsburgh, Pennsylvania 15213, USA
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a)
Electronic mail: jkitchin@andrew.cmu.edu.
J. Chem. Phys. 134, 104709 (2011)
Article history
Received:
December 20 2010
Accepted:
February 10 2011
Citation
Spencer D. Miller, Nilay İnoğlu, John R. Kitchin; Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces. J. Chem. Phys. 14 March 2011; 134 (10): 104709. https://doi.org/10.1063/1.3561287
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