Adsorption energy (eV/O) vs coverage (ML) for oxygen adsorption on the Rh, Ir, Pd, Pt, Cu, Ag, and Au(111) surfaces for 20 configurations.
Atom projected density of states for five configurations of O on Pd(111) with coverages varying from 0 ML (bottom) to 1.0 ML (top). The density of states of the surface metal d-bands, averaged over all surface metal atoms, are shown with grey filling up to the Fermi level. The density of states of the s-p orbitals of the adsorbates, averaged over each adsorbate, is shown as a dashed line with no filling. The d-band center, defined as the first moment of the d-band, is shown as a vertical line for each configuration. The number of electrons in the valence d-band (N), calculated by integration of the density of states up to the Fermi level, is shown for each configuration.
The d-band width vs the d-band center for O on Rh, Ir, Pd, Pt, Cu, Ag, and Au(111) demonstrating the linear dependence expected from the rectangular band model.
Adsorption energy vs the d-band center for O on Rh, Ir, Pd, and Pt(111) demonstrating the linear dependence expected from the Hammer–Nørskov model.
Adsorption energy vs the d-band center for O on Cu, Ag, and Au(111) demonstrating that despite a fully filled valence d-band the linear dependence expected from the Hammer–Nørskov model is still present. The coefficient of determination (R 2) values for the linear fits are 0.71 for Cu, 0.71 for Au, and 0.30 for Ag.
The configurational correlation: the adsorption energy of each configuration of O on Rh, Ir, Pt, Cu, Ag, and Au(111) plotted against the energy of the same configuration on Pd(111), with best fit lines shown for each metal.
Example reconstruction: the Cu configuration is shown on the left, and the Pd configuration is shown on the right, with the oxygen adsorbates appearing as the smaller atoms near the surface (at the top of each configuration). One of the Cu surface metal atoms has lifted out of the surface during relaxation resulting in geometrically dissimilar relaxed configurations.
The configurational correlation for O on Cu(111) vs Pd(111) for both geometrically similar and dissimilar Cu configurations.
Parameters [characteristic radii (r d ) and fractional filling of the valance d-band (f)] for use in model for prediction of configurational correlation slope [Eq. (2)] with the predicted slope (m model), the slope calculated from the DFT results (m DFT), and the difference between the slopes (|Δm|).
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