Reconstruction of charged surfaces: General trends and a case study of Pt(110) and Au(110)
- 18 December 2003
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review B
- Vol. 68 (24), 245416
- https://doi.org/10.1103/physrevb.68.245416
Abstract
The stability of missing-row reconstructions of (110) surfaces with respect to surface charging has been investigated using ab initio theory, taking Pt and Au as representative systems. A thermodynamic formulation is derived to compare the relative stability of charged surfaces either in constant-potential or constant-charge mode. By generalizing Koopmans’ theorem to charged metallic surfaces, we obtain an expression for the surface (excess) energy as a function of charge (or potential) in terms of the neutral surface energy, work function, and the position of the image plane. A surface is shown to reconstruct in constant-charge mode if and only if it reconstructs in constant-potential mode. We next address the question of whether a positive (negative) surface charge can lift (induce) the reconstruction, as suggested in the literature. This turns out not to be the case. Instead the following consistent picture arises: at small surface charges, the effect of the charge follows the difference of the work functions; i.e., positive charge favors a surface having a smaller work function and vice versa. Larger charges, either positive or negative, tend to stabilize the reconstructed surface or, more generally, the reconstruction with larger r. The latter essentially results in that the reconstruction in either Pt or Au is never lifted in our study, although the surface in Au eventually becomes more stable.
Keywords
This publication has 59 references indexed in Scilit:
- Surface embedded atom model of the electrolyte-metal interfacePhysical Review B, 2001
- Work-function anisotropy in noble metals: Contributions fromdstates and effects of the surface atomic structurePhysical Review B, 2000
- Surface relaxation and stress of fcc metals: Cu, Ag, Au, Ni, Pd, Pt, Al and PbModelling and Simulation in Materials Science and Engineering, 1999
- Electronic Effects in the Electric Double LayerChemical Reviews, 1996
- Anisotropy of the stress on fcc(110) surfacesPhysical Review B, 1995
- Surface structure of gold and silver (110)-surfacesElectrochimica Acta, 1995
- Charge induced (1×3) reconstruction of the Au(110) surface: An x-ray scattering studyPhysical Review Letters, 1992
- Structure and mechanism of alkali-metal-induced reconstruction of fcc (110) surfacesPhysical Review B, 1987
- Missing-row surface reconstruction of Ag(110) induced by potassium adsorptionPhysical Review Letters, 1987
- Anisotropy of the Electronic Work Function of MetalsPhysical Review B, 1941