STRUCTURAL AND VIBRATIONAL PROPERTIES OF CARBON MONOXIDE ADLAYERS ON THE COPPER (001) SURFACE

The structure and vibrational states of a prototype adsorbate-substrate system—carbon monoxide on the copper (001) surface—have been calculated from first principles within local density functional theory. Three CO coverages have been examined: θ=0 (bare surface), 0.5, and 1. These systems are represented by a well converged slab model within which all atomic degrees of freedom are treated on an equal footing. The computed structural relaxations and vibrational frequencies are generally in excellent quantitative agreement with the available experimental measurements. The full monolayer is found to be energetically favorable to the half monolayer plus free CO molecule. This indicates that the maximum stable coverage is greater than θ=0.5, in agreement with experiment. The vibrational analysis reveals that resonant coupling between adsorbate and substrate motions has a profound effect on the vibrational spectra, for example, the low-frequency, in-plane frustrated translational motion of the CO molecules mix...

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