Electronic couplings between PEDOT chains. Figure shows that with increasing sorbitol concentration, the PEDOT-PEDOT pair distribution function shows a pronounced peak at low distances. To compute the effect of this short term order on charge transport, we computed the electronic couplings between pairs of PEDOT oligomers in morphologies with varying sorbitol concentration. The results shown in Figure indicate that improved alignment of PEDOT chains at high sorbitol concentration leads to an increase of high electronic couplings in the order of 0.1 eV and above. Electronic couplings of this value are in the same order of magnitude as typical reorganization energies of organic semiconductors which can lead to a delocalization of electronic states beyond the "small/localized polaron" picture, in which Marcus theory is valid. This delocalization can lead to a significant increase in charge carrier mobility as well as to changes of the temperature dependence, which is in particular observed in organic crystals such as rubrene. 44