Effect of Infrared Pulse Excitation on the Bound Charge-Transfer State of Photovoltaic Interfaces

The nature and dynamics of the bound charge-transfer (CT) state in the exciton dissociation process in organic solar cells are of critical importance for the understanding of these devices. It was recently demonstrated that this state can be probed by a new experiment in which an infrared (IR) push-pulse is used to dissociate charges from the bound excited state. Here we proposed a simple quantum dynamics model to simulate the excitation of the IR pulse on the bound CT state with model parameters extracted from quantum chemical calculations. We show that the pulse dissociates the CT state following two different mechanisms: one, fairly expected, is the direct excitation of higher energy CT states leading to charge separation; the other, proposed here for the first time, is a rebound mechanism in which the negative charge is transferred in the opposite direction to form the neutral Frenkel exciton state from where it dissociates.