On the accuracy of first-principles lateral interactions: Oxygen at Pd(100)

Abstract

We employ a first-principles lattice-gas Hamiltonian (LGH) approach to determine the lateral interactions between O atoms adsorbed on the Pd(100) surface. With these interactions we obtain an ordering behavior at low coverage that is in quantitative agreement with experimental data. Uncertainties in the approach arise from the finite LGH expansion and from the approximate exchange-correlation (xc) functional underlying the employed density-functional theory energetics. We carefully scrutinize these uncertainties and conclude that they primarily affect the on-site energy, which rationalizes the agreement with the experimental critical temperatures for the order-disorder transition. We also investigate the validity of the frequently applied assumption that the ordering energies can be represented by a sum of pair terms. Restricting our LGH expansion to just pairwise lateral interactions, we find that this results in effective interactions which contain spurious contributions that are of equal size, if not larger than any of the uncertainties e.g. due to the approximate xc functional.

arXiv comment14 pages including 7 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.html

References in corpus (6)

• Composition, structure and stability of RuO_2(110) as a function of oxygen pressure
• Island nucleation in thin-film epitaxy: A first-principles investigation
• The Pd(100)-(SQRT(5) x SQRT(5) R27^o)-O surface oxide revisited
• Towards a first-principles theory of surface thermodynamics and kinetics
• Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions
• Comparison of the full-potential and frozen-core approximation approaches to density-functional calculations of surfaces

Cited by in corpus (14)

• A Practical Guide to Surface Kinetic Monte Carlo Simulations
• Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces
• Multiple Phase Transitions in Extended Hard Core Lattice Gas Models in Two Dimensions
• CO oxidation on Pd(100) vs. PdO(sqrt5xsqrt5)R27^o: First-Principles Kinetic Phase Diagrams and Bistability Conditions
• Multi-Lattice Kinetic Monte Carlo Simulations from First-Principles: Reduction of the Pd(100) Surface Oxide by CO
• Liquid-Hextic-Solid Phase Transition of a Hard-Core Lattice Gas with Third Neighbor Exclusion
• Estimating the Critical Parameters of the Hard Square Lattice Gas Model
• First-principles statistical mechanics approach to step decoration at surfaces
• Structure Sensitivity in Oxide Catalysis: First-Principles Kinetic Monte Carlo Simulations for CO Oxidation at RuO${}_2$(111)
• The freezing phase transition in hard core lattice gases on triangular lattice with exclusion up to seventh next-nearest neighbor
• Island formation without attractive interactions
• First-principles lattice-gas Hamiltonian revisited: O-Pd(100)
• On Boltzmann Averaging in Ab Initio Thermodynamics
• Adatom pair distribution up to half coverage: O-Pd(100)