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The lowest charge-transfer excited state (CT1) of electron donor–acceptor crystals or polymers is demonstrated to be a plausible precursor of free charge carriers when such materials are photoexcited. Rate constants for the dissociation of charge–transfer states are formulated for two approximate descriptions of CT1: classical ion pair and Wannier exciton. The electric field dependence of the dissociation rate constant is postulated to be given by Onsager’s 1934 theory (O-34) of ion pair dissociation. This formulation of CT1 dissociation obviates the need to invoke electron–hole ‘‘thermalization’’ lengths of 2 to 3 nm in order to explain free charge carrier formation in donor–acceptor materials.
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Charles L. Braun (1984) studied this question.
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