Phonon-Assisted Ultrafast Charge Separation in a Realistic PCBM Aggregate

Abstract: Organic solar cells must separate strongly bound electron-hole pairs into free charges. This is achieved at interfaces between electron donor and acceptor organic semiconductors. The most popular electron acceptor is the fullerene derivative PCBM. Electron-hole separation has been observed on femtosecond timescales, which is incompatible with conventional Marcus theories of organic transport. In this work we show that ultrafast charge transport in PCBM arises from its broad range of electronic eigenstates, provided by the presence of three closely spaced delocalised bands near the LUMO level. Vibrational fluctuations enable rapid transitions between these bands, which drives an electron transport of $\sim$3 nm within 100 fs. All this is demonstrated within a realistic tight binding Hamiltonian containing transfer integrals no larger than 8 meV.