The reactivity of heterogeneous catalysts under working conditions may be strongly influenced by adsorbate-adsorbate interactions which alter reaction barriers and lead to the formation of ordered adsorbate structures like islands. To predict catalytic reactivity, accurate knowledge of adsorbate-adsorbate interaction energies is required, but it is rarely available. One challenge arises from the surprisingly long range over which these interactions exert influence. We show in this work-using DFT with periodic boundary conditions and an (8 × 8) unit cell-that a single O-atom adsorbed at Pt(111) induces significant Pt atom displacements out to more than 7 Å. This adsorbate induced surface strain allows O*-atoms at distances of 14 Å to experience repulsion between one another due to the adsorbate induced displacement of the Pt atoms between them. Similar calculations using smaller unit cells overestimate repulsion due to interactions between O* atoms in neighboring periodic images. The use of an (8 × 8) unit cell removes this error, revealing short range attractive interactions between 3rd nearest neighbors. We have used these improved DFT interaction energies to perform kinetic Monte Carlo simulations of oxygen island formation and to show how the interplay of short- and long-range forces determines the sizes and shapes of these islands. Neglect of long-range interactions leads to round and compact island structures, which are in conflict with STM experiments. Including all interactions out to the 9th nearest-neighbor results in simulations that eerily resemble the STM observations.
Nitz et al. (Wed,) studied this question.