High-purity ultrathin layers of Pu deposited on Mg were studied by X-ray ph
otoelectron (XPS) and high-resolution valence band (UPS) spectroscopy. The
itinerant character of the 5f states is gradually lost with reduced thickne
ss, and the localised 5f states, which appear as a broad peak 1.6 eV below
the Fermi level, were observed for one monolayer. At intermediate thickness
three narrow peaks appear close to the Fermi level, which are identical to
features observed in PuSe and other Pu materials. A comparative study of b
ulk alpha -Pu indicates a surface re-organisation yielding more localised f
-electrons at conditions of thermodynamic equilibrium.