We calculated the energy landscape of charged molecules that is determined by electrostatic and induction interaction using the fully polarizable force field DRF90 in the bulk and at interfaces of the electron accepting material C60, and two exemplary electron donating materials pentacene and phthalocyanine. In particular, we compared the energy of a non-interacting electron-hole pair (NI-EH) without mutual electrostatic interactions to the energy of a Coulomb-bound interfacial charge-transfer state (CT). Our calculations show that due to electrostatic interactions with the environment a NI-EH state is destabilized on the phthalocyanine-C60 interface, whereas it is stabilized on the interface between pentacene and C60, even without the interaction with the counter charge. Upon adding the mutual electrostatic interaction between the opposite charges the electrostatic term overall stabilizes the CT state in both systems. This stabilization is not compensated by the reduced induction term. The resulting binding energy of the CT state amounts to several tenths of an eV, which contradicts the evidence of working solar cells based on these systems. The overestimated CT state binding energy for charges localized on a single molecule suggests that charge delocalization over multiple molecules might play an important role. Nevertheless, our results indicate clear opportunities to engineer electrostatic interactions at the interface that might lead to destabilization of NI-EH and hence to a lower binding energy of CT

This work was supported by the Netherlands Organization for Scientific Research (NWO) through an VIDI grant to FCG and by the European Research Council (ERC) in the form of ERC Starting Grant to FCG. The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, project number CTQ2011-25086/ BQU) and the DIUE of the Generalitat de Catalunya (project number 2009SGR528, and Xarxa de Referencia en Quimica Teorica i Computacional)