Separation of the attractive and repulsive contributions to the adsorbate–adsorbate interactions of polar adsorbates on Si(100)

Abstract Dissociative adsorption of H 2 O, NH 3 , CH 3 OH and CH 3 NH 2 polar molecules on the Si(100) surface results in a 1:1 mixture of two adsorbates (H and multi-atomic fragment A = OH, NH 2 , CH 3 O, CH 3 NH, respectively) on the surface. By using density functional theory (DFT) calculations, the adsorption geometry, the total energies and the charge densities for various possible ordered structures of the mixed adsorbate layer have been found. Analyzing the systematic trends in the total energies unveils concurrently the nearest-neighbor interactions E NN and the next nearest-neighbor interactions E NNN between two polar adsorbates A. In going from small to large polar adsorbates, E NN 's exhibit an attractive-to-repulsive crossover behavior, indicating that they include competing attractive and repulsive contributions. Exploration of the charge density distributions allows the estimation of the degree of charge overlapping between immediately neighboring A's, the resulting contribution of the steric repulsions, and that of the attractive interactions to the corresponding E NN 's. The attractive contributions to nearest neighboring adsorbate–adsorbate interactions between the polar adsorbates under study are shown to result from hydrogen bonds or dipole–dipole interactions.