Interactions Mediated by Surface States: From Pairs and Trios to Adchains and Ordered Overlayers

TL;DR

This paper develops a quantitative formalism for analyzing surface-state mediated interactions among adatoms, extending previous pair interaction models to include three-body effects and applying it to ordered overlayers and linear defects.

Contribution

It introduces a formalism for calculating full indirect interactions, including non-pairwise contributions, on noble metal surfaces, and relates these to experimental observations of adatom behavior.

Findings

Excellent agreement with experimental pair interaction data

Extended formalism to include three-adsorbate interactions

Insights into adatom motion and step interactions on vicinal surfaces

Abstract

Since metallic surface states on (111) noble metals are free-electron like, their propagators can be evaluated analytically. Since they are well-screened, one can use simple tight-binding formalism to study their effects. The needed phase shifts can be extracted from experiment. Hence, one can now make quantitative predictions of these slowly-decaying, oscillatory indirect interactions. For the (isotropic!) pair interactions (which decay as the inverse square of adatom-adatom separation), remarkable agreement has been obtained with experiments by two groups. We have extended the formalism to consider the full indirect ("triple") interaction of 3 adsorbates, which is the sum of the 3 constituent pair interactions plus the non-pairwise "trio" contribution, which tends to decay with the 5/2 power of perimeter. Here, we concentrate on interactions due to ordered overlayers and to linear defects, relating the latter to the interactions of (nx1) ordered overlayers and to the constituent pair interactions. We compare with experimental studies of interactions of adatoms with adchains and of consequent 1D motion of adatoms trapped between two such parallel chains. We discuss implications for step-step interactions (on vicinal surfaces), with attention to the modification of the surface state itself for small terrace widths.