Nonadiabatic dynamics of charge transfer and singlet fission at the pentacene/C₆₀ interface

Charge carrier multiplication in organic heterojunction systems, a process known as singlet fission (SF), holds promise for development of solar cells with enhanced photon-to-electron yields, and therefore it is of substantial fundamental interest. The efficiency of photovoltaic devices based on this principle is determined by complex dynamics involving key electronic states coupled to particular nuclear motions. Extensive experimental and theoretical studies are dedicated to this topic, generating multiple opinions on the nature of such states and motions, their properties, and mechanisms of the competing processes, including electron-phonon relaxation, SF, and charge separation. Using nonadiabatic molecular dynamics, we identify the key steps and mechanisms involved in the SF and subsequent charge separation, and build a comprehensive kinetic scheme that is consistent with the existing experimental and theoretical results. The ensuing model provides time scales that are in excellent agreement with the experimental observations. We demonstrate that SF competes with the traditional photoinduced electron transfer between pentacene and C₆₀. Efficient SF relies on the presence of intermediate dark states within the pentacene subsystem. Having multiexciton and charge transfer character, these states play critical roles in the dynamics, and should be considered explicitly when explaining the entire process from the photoexcitation to the final charge separation.