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A quantitative analysis of the surface composition of the Heusler alloy NiMnSb has been undertaken using angle-resolved x-ray photoemission spectroscopy and the surface composition characterized. With sufficient annealing cycles, the stoichiometric surface evolves to a surface that is manganese rich. This indicates that the surface enthalpy is different from the bulk for the Heusler alloy NiMnSb. ©2000 American Institute of Physics.