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Cs2O2 is alpha boron-derived structured and crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. Cs is bonded in a 6-coordinate geometry to six equivalent O atoms. There are four shorter (2.98 Å) and two longer (3.20 Å) Cs–O bond lengths. O is bonded in a 7-coordinate geometry to six equivalent Cs and one O atom. The O–O bond length is 1.52 Å.
Cs2O2 is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cs is bonded to six equivalent O atoms to form a mixture of corner and edge-sharing CsO6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cs–O bond lengths are 3.03 Å. O is bonded to six equivalent Cs atoms to form a mixture of corner and edge-sharing OCs6 octahedra. The corner-sharing octahedral tilt angles are 0°.
Cesium carbonate (Cs2CO3) was heated to the decomposition temperature of approximately 600 C. The nonvolatile decomposition products were condensed on a nickel substrate while the carbon dioxide was removed by pumping. The deposited material is characterized by an effective work function of between 1.05 and 1.15 eV at 450 K and by photoemission in the visible and near-infrared region of the spectrum. It is suggested that the deposited material consists of Cs2O, possibly Cs2O2, and adsorbed cesium. Silver, evaporated from a heated silver bead, produced the typical photoemissive and thermionic properties of a silver-oxygen-cesium (S-1) photocathode. The material may be of interest for thermionic energy converters and for the formation of silver-oxygen-cesium photocathodes.