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X-ray photoelectron spectroscopy (XPS) is used to measure splittings of metal-atom electron binding energies, in both inorganic solids and gases. These splittings are due to the various possible multiplet states formed by coupling a hole in a metal-atom subshell to an unfilled valence subshell. Splittings are observed in various solids containing 3d series atoms, In particular, the 3s binding energy is split into a doublet with as much as 7.0 eV separation between the two components. The.instrQ~ental resolution is ~ 1.0 eV. 3s splittings are exhibited by inorganic compounds containing Mn and Fe, as well as by Fe metal, Co metal, and Ni metal. Theoretical predictions are in good agreement with experiment, provided that the effects of covalency in chemical bonding are taken into account. For Fe metal, the 3s splitting is identical both above and below the Curie point. The 3p binding energies of these solids also appear to show m~ltiplet effects, but the interpretation of these results is less straightforward. The 2p bind:Lng energies in f-.1nF 2 are broadened by at least 1. 3 eV, and this is sho•m to be consistent with multiplet splitting. XPS results for gaseous monatomic Eu also indicate the presence of multiplet splittings. 'l'he tva components in the 4d photoelectron

Multiplet Splitting of Metal-Atom Electron Binding Energies