Alloying Au into the outermost atomic layer of Ni(111) significantly alters the physical and chemical properties of the surface. The reactivity is investigated by the use of seeded supersonic molecular beams of CH4 and it is found that the nobleness of Au reduces the overall reactivity toward CH4. This is accounted for in an ensemble model resolving the sticking probability on Ni atoms having different nearest neighbor surroundings. Although a mean field description of site distributions is found to be a very good approximation it is improved by using experimentally determined ensemble statistics from STM images. The strong influence of the vibrational temperature on the sticking coefficients of CH4 vs translational energy on the pure Ni(111) is also demonstrated. Desorption energies of CO and D-2 is observed to decrease approximately 25-30 kJ/mole as the coverage of Au is increased from 0.0 to 0.7 ML. In TPD spectra of deuterium saturated surface alloys a new clearly resolved desorption state is observed at 180-220 K with maximum intensity around theta(Au)=0.3-0.4 ML. This state is clearly related to chemisorption sites involving both Au and Ni. A site model based on mean field statistics adequately accounts for the appearance of this state. The effect of Au is also evident in the TPD spectra of CO saturated Au/Ni(111) surface alloys where the saturation coverage decreases and new structure develops. (C) 1996 American Institute of Physics.
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