Nature of the O-fcc(110) Surface-Bond Networking

Abstract

New insight into the nature and formation of the multiphase ordering of oxygen onto threefold sites of fcc(110) (Rh, Pd and [Formula: see text] analogue) is presented. By including bond-to-band model and the potential-barrier for oxygen-metal chemisorption with theoretical and experimental observations, it is shown that the multiphase ordering, composed of (2×1)pmg, (2×1)p2mg and (2×2)p2mg structures, originates from the hybridized- O -2 forming at different oxygen coverages with a specific bonding environment. Unlike the long-bridge sited O -2 ions on the Cu(Ni, Ag)(110) which give the missing-row type reconstruction, the threefold-coordinated O -2 ions on the Rh(Pd)(110) form a tetrahedron through one bond to the metal atom underneath and two nonbonding lone pairs acting on its two neighbors in the first layer. In the (2×1)p2mg structure, the lack of one metal atom for the tetrahedron is compensated by a virtual bond pulling the electron-cloud of the dipoles that are induced by the lone pairs of other O -2 ions. The tetrahedron in the (2×2)pg structure requires an electron from a metal atom in the next nearest row at the surface. Therefore, the bond network interlocks all the surface atoms; and thereby, no atoms are missing. The zigzag protrusions in the STM images are recognized as metal dipoles deformed by the lone pairs of O -2 ions. The depressions correspond to rows of M + metal ions other than missing-row vacancies as had been expected previously.