Ziyao Xu, Yi Zhou, Lynn Groß, Antonietta De Sio, Chi Yung Yam, Christoph Lienau*, Thomas Frauenheim, GuanHua Chen*
Nano Letters (2019) 19(11), pp. 8630-8637
There is growing experimental and theoretical evidence that vibronic couplings, couplings between electronic and nuclear degrees of freedom, play a fundamental role in ultrafast excited-state dynamics in organic donor-acceptor hybrids. Whereas vibronic coupling has been shown to support charge separation at donor-acceptor interfaces, so far, little is known about its role in the real-space transport of charges in such systems. Here we theoretically study charge transport in thiophene:fullerene stacks using time-dependent density functional tight-binding theory combined with Ehrenfest molecular dynamics for open systems. Our results reveal coherent oscillations of the charge density between neighboring donor sites, persisting for ∼200 fs and promoting charge transport within the polymer stacks. At the donor-acceptor interface, vibronic wave packets are launched, propagating coherently over distances of more than 3 nm into the acceptor region. This supports previous experimental observations of long-range ballistic charge-carrier motion in organic photovoltaic systems and highlights the importance of vibronic coupling engineering as a concept for tailoring the functionality of hybrid organic devices.