The photoelectron spectroscopy of HO2 and DO2 has been studied. We find the electron affinities (E.A.) of the corresponding radicals to be E.A.(HO2)=1.078±0.017 eV and E.A.(DO2)=1.089±0.017 eV; the gas phase acidity of hydrogen peroxide is ΔHacid (HO2–H) =376.4 ±0.6 kcal/mol. The electron spectra show only one active mode which we assign as the HO–O stretch (ω3). By modeling the Franck–Condon factors we deduce a molecular structure for the HO2 ion: r0(HO–O)=1.50 Å, r0(H–OO)=0.97 Å, and ∠(H–O–O)=104°. A parallel set of GVB/PP, GVB‐CI, and POL‐CI abinitio electronic structure computations has been carried out for this ion.

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