We introduce the concept that free-charge generation in organic photovoltaic (OPV) materials may best be described by competition between long- and short-range electron transfer events, and that the distribution of rates as a function of distance follows the predictions of Marcus theory. Our results reveal the fundamental connection between solution-phase electron transfer research that has been conducted in the chemistry community over many decades, and the younger materials science effort to develop efficient OPV materials. The model that emerges provides insight into how the microstructure of OPV materials influences the electron transfer process via both entropic and quantum-mechanical mechanisms.
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