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Monomer and dimer radical cations of isoprene, eis‐ and trans‐1,3‐pentadiene, 1,3‐cyclohexadiene, 1,4‐cyclohexadiene, and 1,5‐cyclooctadiene were observed in n‐butyl chloride solution after electron pulse irradiation. The optical absorption spectra of diene monomer radical cations obtained by pulse radiolysis compare well with spectra measured in γ‐irradiated matrices [1, 2]. Diene monomer radical cations are formed by charge transfer from n‐butyl chloride radical cations with rate constants between 5 and 10 · 109 dm3 mol−1 s−1. From the decay of the corresponding diene monomer cation absorption rate constants of the dimerization reaction were determined. The diene dimer radical cation bands were identified by their kinetic behaviour in a wide temperature range. Spectroscopical assignments of the absorption bands are discussed.

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