Photo-predissociation dynamics of rotational states (N) of OH (A2Σ+=3 and 4) are studied using high-n Rydberg atom time-of-flight technique. Spin–orbit branching fractions of O(3PJ=2,1,0) are measured: 0.676±0.010:0.138±0.013:0.186±0.017 for N=0 in ν=3 and 0.873±0.026:0.102±0.028:0.025±0.005 for N=0 in ν=4, in excellent agreement with the recent theory. While OHA2Σ+ν=3 predissociates predominantly via a single 4Σ state, ν=4 decays via the Σ4, Σ2, and Π4 states, and interferences of these dissociation pathways strongly influence the O(3PJ) fine-structure distributions. D0(O–H)=35 565±30 cm−1 is obtained.

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