Seventh‐order anti‐Stokes Raman‐shifted ultraviolet laser radiation is used to dissociate O2 in the 175–177 nm region of the Schumann–Runge band system, B3ΣuX3Σg. A cross section for the production of O(1D2) is deduced from the 762 nm fluorescence of O2(b1Σ+g), a collisional de‐excitation product of O(1D2) and O2(X3Σg). Step structure observed in the spectrum is attributed to rotational thresholds for absorption from X3Σg to energies above the B3Σu dissociation limit. The threshold energies define a limiting rotationless dissociation energy of 57 136.4±0.9 cm−1. Shape resonances, quasibound by the rotational barrier of B3Σu, are observed for the first time in O2. A theoretical calculation of the cross section is in agreement with the measured cross section when the near‐dissociation outer limb of the B3Σu potential has an R−5 long range form. The shape of the adopted potential is consistent with an avoided crossing with another 3Σu state near R=4.6 Å.

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