Reconstruction Mechanism of FCC Transition-Metal (001) Surfaces

The reconstruction mechanism of (001) fcc transition metal surfaces is investigated using a full-potential all-electron electronic structure method within density-functional theory. Total-energy supercell calculations confirm the experimental finding that a close-packed quasi-hexagonal overlayer reconstruction is possible for the late 5$d$-metals Ir, Pt, and Au, while it is disfavoured in the isovalent 4$d$ metals (Rh, Pd, Ag). The reconstructive behaviour is driven by the tensile surface stress of the unreconstructed surfaces; the stress is significantly larger in the 5$d$ metals than in 4$d$ ones, and only in the former case it overcomes the substrate resistance to the required geometric rearrangement. It is shown that the surface stress for these systems is due to $d$ charge depletion from the surface layer, and that the cause of the 4th-to-5th row stress difference is the importance of relativistic effects in the 5$d$ series.Comment: RevTeX 3.0, 12 pages, 1 PostScript figure available upon request] 23 May 199