The photoionization efficiencies of the ions F2O+ and OF+ have been measured in a photoionization mass spectrometric study of F2O. The adiabatic first ionization potential of F2O is determined to be 13.11 ± 0.01 eV. The region near threshold (13.11–13.6 eV) has structure that is interpreted as vibrational autoionization. Additional peaks at 13.81, ∼ 15, and ∼ 15.5 eV are interpreted as Rydberg levels that decay by an electronic autoionization mechanism and which converge to the second ionization potential at 16.17 eV. An upper limit for the appearance potential of OF+(0°K) is found to be 14.438 eV, grossly different from the electron impact value of 15.8 ± 0.2 eV. The current result implies Δ H°f0(OF)=+26.1 ± 2.3 kcal/mole and I.P.(OF)=12.79 ± 0.10eV.

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