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A harmonic force field for difluorodioxirane was derived from fundamental wavenumbers, isotopic shifts, centrifugal distortion constants, and inertial defect differences. The following geometric structure was determined by a joint analysis of gas electron diffraction intensities and rotational constants of the parent species (rz values with 1σ uncertainties):  O−O = 1.578(1), C−O = 1.348(8), C−F = 1.317(6) Å, ∠FCF = 108.8(7)°. The extremely long O−O bond correlates with the small force constant of 2.94 × 102 N m-1.

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