Influence of adatom interactions on second layer nucleation

We develop a theory for the inclusion of adatom interactions in second layer nucleation occurring in epitaxial growth. The interactions considered are due to ring barriers between pairs of adatoms and binding energies of unstable clusters. The theory is based on a master equation, which describes the time development of microscopic states that are specified by cluster configurations on top of an island. The transition rates are derived by scaling arguments and tested against kinetic Monte-Carlo simulations. As an application we reanalyze experiments to determine the step edge barrier for Ag/Pt(111).Comment: 4 pages, 4 figure

Nature, strength, and consequences of indirect adsorbate interactions on metals

Atoms and molecules adsorbed on metals affect each other indirectly even over considerable distances. Via systematic density-functional calculations, we establish the nature and strength of such interactions, and explain for what adsorbate systems they critically affect important materials properties. This is verified in kinetic Monte Carlo simulations of epitaxial growth, which help rationalize a number of recent experimental reports on anomalously low diffusion prefactors

Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions

Previous and present "academic" research aiming at atomic scale understanding is mainly concerned with the study of individual molecular processes possibly underlying materials science applications. Appealing properties of an individual process are then frequently discussed in terms of their direct importance for the envisioned material function, or reciprocally, the function of materials is somehow believed to be understandable by essentially one prominent elementary process only. What is often overlooked in this approach is that in macroscopic systems of technological relevance typically a large number of distinct atomic scale processes take place. Which of them are decisive for observable system properties and functions is then not only determined by the detailed individual properties of each process alone, but in many, if not most cases also the interplay of all processes, i.e. how they act together, plays a crucial role. For a "predictive materials science modeling with microscopic understanding", a description that treats the statistical interplay of a large number of microscopically well-described elementary processes must therefore be applied. Modern electronic structure theory methods such as DFT have become a standard tool for the accurate description of individual molecular processes. Here, we discuss the present status of emerging methodologies which attempt to achieve a (hopefully seamless) match of DFT with concepts from statistical mechanics or thermodynamics, in order to also address the interplay of the various molecular processes. The new quality of, and the novel insights that can be gained by, such techniques is illustrated by how they allow the description of crystal surfaces in contact with realistic gas-phase environments.Comment: 24 pages including 17 figures, related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Atom-by-Atom and Concerted Hopping of Adatom Pairs on an Open Metal Surface

Atom-by-atom and concerted hopping of ad-dimers on the open (100) surface of fcc metals are studied by means of density-functional calculations. The adatom interaction is relatively short-ranged, and beyond next-nearest neighbors ad-dimers are effectively dissociated. Diffusion takes place by a simple shearing process, favored because it maximizes adatom coordination at the transition state This holds for Al, Au, and Rh, and is likely a general result because geometrical arguments dominate over details of the electronic structure

Nature, strength, and consequences of indirect adsorbate interactions on metals

Atoms and molecules adsorbed on metals affect each other even over considerable distances. In a tour-de-force of density-functional methods, the authors establish the nature and strength of such indirect interactions, and explain for what adsorbate systems they can critically affect important materials properties. These perceptions are verified in kinetic Monte Carlo simulations of epitaxial growth, and help rationalize a cascade of recent experimental reports on anomalously low diffusion prefactors. The authors focus their study on two metal systems: Al/Al(111) and Cu/Cu(111)