Interplay between steps and nonequilibrium effects in surface diffusion for a lattice-gas model of O/W(110)

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School of Science | A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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The Journal of Chemical Physics, Volume 126, Issue 11
The authors consider the influence of steps and nonequilibrium conditions on surfacediffusion in a strongly interactingsurfaceadsorbate system. This problem is addressed through Monte Carlo simulations of a lattice-gas model of O∕W(110), where steps are described by an additional binding energy EB at the lower step edge positions. Both equilibrium fluctuation and Boltzmann-Matano spreading studies indicate that the role of steps for diffusion across the steps is prominent in the ordered phases at intermediate coverages. The strongest effects are found in the p(2×1) phase, whose periodicity Lp is 2. The collective diffusion then depends on two competing factors: domain growth within the ordered phase, which on a flat surface has two degenerate orientations [p(2×1) and p(1×2)], and the step-induced ordering due to the enhanced binding at the lower step edge position. The latter case favors the p(2×1) phase, in which all adsorption sites right below the step edge are occupied. When these two factors compete, two possible scenarios emerge. First, when the terrace width L does not match the periodicity of the ordered adatom layer (L/Lp is noninteger), the mismatch gives rise to frustration, which eliminates the effect of steps provided that EB is not exceptionally large. Under these circumstances, the collective diffusion coefficient behaves largely as on a flat surface. Second, however, if the terrace width does match the periodicity of the ordered adatom layer (L/Lp is an integer), collective diffusion is strongly affected by steps. In this case, the influence of steps is manifested as the disappearance of the major peak associated with the ordered p(2×1) and p(1×2) structures on a flat surface. This effect is particularly strong for narrow terraces, yet it persists up to about L≈25Lp for small EB and up to about L≈500Lp for EB, which is of the same magnitude as the bare potential of the surface. On real surfaces, similar competition is expected, although the effects are likely to be smaller due to fluctuations in terrace widths. Finally, Boltzmann-Matano spreading simulations indicate that even slight deviations from equilibrium conditions may give rise to transient peaks in the collective diffusion coefficient. These transient structures are due to the interplay between steps and nonequilibrium conditions and emerge at coverages, which do not correspond to the ideal ordered phases.
diffusion, adsorption, collective models, Monte Carlo methods, strong interactions
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Masin, M. & Vattulainen, I. & Ala-Nissilä, Tapio & Chvoj, Z. 2007. Interplay between steps and nonequilibrium effects in surface diffusion for a lattice-gas model of O/W(110). The Journal of Chemical Physics. Volume 126, Issue 11. 114705/1-8. 1089-7690 (electronic). 0021-9606 (printed). DOI: 10.1063/1.2713100.