We report the rotationally resolved, one‐photon threshold photoelectron spectrum of the methyl radical, CH3, produced by supersonic‐jet, flash pyrolysis. Only rotational transitions with ΔK=0, ±2 are observed and this result is shown to be consistent with photoionization selection rules in D3h symmetry. Assignment of the threshold photoelectron spectrum results in an adiabatic ionization potential of 79 349±3 cm−1.

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