The photoion yield curves of HOBr+ and Br+ from HOBr are presented. The adiabatic I.P. of HOBr is found to be 10.638±0.003 eV. Autoionizing structure in HOBr+ is tentatively assigned and leads to an adiabatic I.P. of the first excited (AL2A′) state of ∼11.46 eV. The 0 K threshold of Br+ from HOBr (13.915±0.018 eV) implies D0(HO–Br)≤2.101±0.018 eV≡48.45±0.42 kcal/mol. Together with auxiliary thermochemistry, this value yields ΔHf2980(HOBr) ≥ −13.43 ± 0.42 kcal/mol, in excellent agreement with a recent abinitio value −14.2±1.6 kcal/mol. The resulting proton affinity of BrO is 163.8 kcal/mol. Trends observed in the properties of OX and HOX (X=F, Cl, Br) are utilized to infer new values for ΔH0f(OI) and ΔH0f (HOI). Predictions are made for I.P.(HOI). Proton affinities of OX are seen to increase with heavier X, while the X2A″–A2A′ splitting decreases.

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