Abstract
One-photon and two-photon resonantly enhanced multiphoton ionization (REMPI) spectra of the Rydberg B state of photonated and deuterated methyl iodide have been obtained at room temperature. In CD 3I, the “CI stretching” vibration (ν 3) is absent from the (2 + 2) REMPI spectrum, but is present in the (1 + 1) spectrum and in both (1 + 1) and (2 + 2) spectra of CH 3I. The absence of this band in the two-photon CD 3I spectrum is explained in terms of the intermediate state dynamics. For a dissociative intermediate excited state in a REMPI experiment, the competition between ionization and dissociation regulates ion production and, therefore, signal intensity. The absence of the ν 3 in the (2 + 2) REMPI spectrum is indicative of its rapid dissociation.
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