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A theoretical analysis is made of the rate of intramolecular transfer of the odd electron between the two phenyl groups in the mononegative ions of the α,ω‐diphenyalkanes, φ—(CH₂)_n—φ. The essential features of the calculations are: (a) It is shown that the polymethylene chain can be replaced by a pseudopotential corresponding to an effective direct transfer between the rings. (b) There is a strong tendency for self‐trapping of the odd electron on one phenyl ring, or the other, due to solvent polarization and bond distortions in the rings. This self‐trapping greatly reduces the rate of intramolecular charge transfer. (c) The intramolecular charge transfer occurs as an electronic resonance effect when a short‐lived thermally activated molecular state is formed in which the two rings appear to the odd electron to be equivalent to one another. The activation energy is estimated to be of the order of 1000 cm^—1. (d) It is found …