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Zusammenfassung:
Atomic nitrogen on Ru(0001) was prepared by dissociative chemisorption of N2 and studied by scanning tunneling microscopy (STM) at 300 K. Nitrogen occupies the hcp threefold hollow site and is imaged as a depression with a diameter of about 5 Å. Interactions between the adsorbed nitrogen atoms were obtained by statistical analysis of STM images, by extraction of the two-dimensional pair distribution function from the arrangement of the N atoms. Since the nearest-neighbor separations could be identified with atomic precision, the pair distribution function g and hence the potential of mean force Veff were obtained as a function of the discrete neighbor sites j up to the tenth nearest neighbor. A comparison with Monte Carlo calculations for balls with a hard-sphere potential provides information about the pair potential Vpair(j): The nearest-neighbor site is strongly repulsive, the second-neighbor site is weakly repulsive, and the third-neighbor site is weakly attractive. These findings rationalize the absence of island formation and of a well-ordered 2×2 phase for the N/Ru(0001) system: At temperatures ≥300 K the attractive interaction on the third-neighbor site is too weak, while at lower temperatures the diffusion barrier of 0.9 eV represents a kinetic obstacle. The fact that the range of the interaction is identical to the diameter of the N-atom features in the STM topographs is taken as evidence that the interaction is caused by substrate-mediated electronic forces.
