Segregation in strongly ordering compounds: a key role of constitutional defects.

For the example of the B2 CoAl(100) surface, we demonstrate that even slight deviations from an ordered alloy's ideal stoichiometry in a subsurface region or in the bulk can drastically affect its surface composition. By experimental surface analysis and first-principles calculations, we show that Co antisite atoms segregate to the very surface, driven by the same strong interactions which enforce order in the bulk. Our findings are consistent with the lack of antisite segregation we found earlier for the much weaker ordering FeAl(100), and resolve contradictory reports for NiAl(100).