Theoretical Study on Thermal Structural Fluctuation Effects of Intermolecular Configurations on Singlet Fission in Pentacene Crystal Models

Singlet fission (SF) occurs as a result of complex excited state relaxation dynamics in molecular aggregates, where a singlet exciton (FE) state is converted into a double-triplet exciton (TT) state through the interactions with several other degrees of freedom, such as nuclear motions. In this study, we combined quantum dynamics simulation based on the quantum master equation approach with all-atom-based classical molecular mechanics/molecular dynamics to examine the thermal structural fluctuation (i.e., static disorder) effects of intermolecular configuration on SF in pentacene crystal models. In particular, we considered two types of static-disordered models, in which excited states are assumed to interact with nuclear motions of intermolecular modes in the classical mechanical/statistical manner. We found that the introduction of static disorder effects leads to a faster decay of coherence between the FE and charge transfer (CT) states in the early stage of SF, contributing to the accelerations of several FE -> TT relaxation pathways. Such acceleration in these models is shown to be attributed to fluctuations in the energies and electronic coupling of the CT states based on relative relaxation factor analysis. The present study is expected to contribute to further development of bottom-up materials design for efficient SF in condensed phases where the exitonic system interacts with nuclear motions in various coupling strengths.