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Using the photoemission of adsorbed xenon technique we demonstrate that the two‐dimensional alloy formation between ordered Ag islands on Ru(001) and Au atoms deposited on top of these islands proceeds via a two‐step mechanism: The Au atoms do not penetrate the Ag layer directly, but first migrate from the islands onto the Ru substrate, from where they then ‘‘attack’’ the Ag islands to form a two‐dimensional AgAu alloy.

Mechanism of two-dimensional AgAu alloy formation on Ru(001)