Nascent CD3 radicals produced by photodissociation of CD3I after absorption of 266 nm radiation by the à state are studied using the photofragment imaging technique. Two‐photon, resonance‐enhanced, multiphoton ionization [(2+1) REMPI] probes CD3 via the 3pz2A2 Rydberg excited electronic state. CD3I photodissociation at 266 nm is found to produce ground‐electronic‐state CD3 radicals with substantial vibrational excitation of the ν2 umbrella mode. Rotational constants are determined for v=0, 1, and 2 of ν2 in the 3pz excited state by analysis of the spectra. A first‐order perturbation and diagonalization procedure is used to generate potential energy curves for the umbrella mode in both the ground and excited electronic states and Franck–Condon factors for various transitions between the states. These results should prove useful when employing REMPI to characterize methyl radicals in many environments.

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