Photoemission studies of clean and oxidized Cs

Photoemission studies of the oxidation of Cs at ～ 140 K have been carried out. Four different states of oxygen were observed. Definitive identification of three of the four states has been achieved in two steps: (1) comparison of the multiplet structure of free oxygen ions and the multiplet structure in the photoemission spectra of oxygen sorbed in Cs (i.e., comparison of the energy separations of the various oxygen levels involved); and (2) comparison of experimentally measured binding energies of various states of oxygen with calculated binding energies of known oxygen species inserted in Cs. The oxygen species identified are O^2?, O₂^2? and O₂^?. The multiplet structure of O₂^2? in Cs is identical to that expected for free O₂^2? with no differential relaxation of orbital energies. In contrast, significant differential relaxation in orbital energies is observed for O₂^? in Cs. This difference is attributed to the closed-shell and open-shell configurations of O₂^2? and O₂^?, respectively. The oxidation-induced changes in the Cs 4d, 5s and 5p core levels and the NOO and OVV Auger transitions have also been studied in detail. A discussion of the oxidation of Cs, based on the oxygen species identified definitively, is also given.