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The composition in the surface region of the Heusler alloy NiMnSb has been studied using angle-resolved X-ray photoemission spectroscopy, low-energy electron diffraction and spin-polarized inverse photoemission. The results are consistent with a generally Mn-Sb terminal layer, though the surface composition is very sensitive to preparation. The surface composition has a critical influence on the polarization near the Fermi level in spin-polarized inverse photoemission. Under some conditions, the polarization at the Fermi level for normal incidence inverse photoemission can reach values very close to 100% above background.