X-ray standing wave measurements, along with local-density molecular cluster calculations, were used to determine the surface structure of the low-coverage Bi/Si(001) surface. The 2×{}2 Bi phase, predicted by theory to be the stable low-coverage structure, was found experimentally to be a metastable phase and was observed to have a thermally activated irreversible phase transition to the stable 1×{}2 phase. These measurements represent another approach for investigating the kinetics of surface reactions. {} 1996 The American Physical Society.
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