First-principles lattice-gas Hamiltonian revisited: O-Pd(100)

TL;DR

This paper revisits the derivation of lattice-gas Hamiltonians from first principles, proposing a long-range elastic interaction model for O-Pd(100) that includes many-body terms and is analytically tractable.

Contribution

It introduces a long-range elastic interaction model with many-body terms for O-Pd(100), improving upon traditional truncation methods in lattice-gas Hamiltonians.

Findings

Long-range elastic interactions are significant for O-Pd(100).

The proposed model uses only 3 parameters fitted to first-principles data.

Analytic nature of the model enables alternative statistical analysis methods.

Abstract

The methodology of deriving an adatom lattice-gas Hamiltonian (LGH) from first principles (FP) calculations is revisited. Such LGH cluster expansions compute a large set of lateral pair-, trio-, quarto interactions by solving a set of linear equations modelling regular adatom configurations and their FP energies. The basic assumption of truncating interaction terms beyond fifth nearest neighbors does not hold when adatoms show longer range interactions, e.g. substrate mediated elastic interactions. O-Pd(100) as a popular reference is used to propose a long range elastic interaction alternative including many-body trio- and quarto terms with just 3 parameters fitted to FP calculations. A key feature of the interaction alternative is its analytic nature, allowing statistical methods different from Monte Carlo simulations to derive surface order. The assumptions made are discussed and ways to further verify and apply the model are outlined.