Modeling the effects of molecular disorder on the properties of Frenkel excitons in organic molecular semiconductors.

The Frenkel exciton model provides a convenient framework for simulating electronic excitations in organic conjugated systems that are too large to address with atomistic level electronic structure methods. Parameterization of this model is typically based on analytical expressions that incompletely describe the spatial and temporal correlations that are inherent to many condensed phase molecular systems. In this manuscript, we present a general procedure for including these correlations in the Frenkel exciton model, by mapping them directly from all-atom molecular configurations, for instance from classical molecular dynamics. Regardless of system morphology, this mapping automatically captures the spatial and temporal molecular correlations that are otherwise difficult or impossible to represent in terms of low-dimensional correlation functions. We apply this procedure to study the excited state properties of condensed phase materials made up of thiophene oligomers. We show that Frenkel model parameters can be mapped from a series of single molecule electronic structure calculations, and that for these materials efficient semi-empirical methods are sufficient to accurately reproduce experimental spectral measurements. By analyzing the statistics of model parameters derived from materials with different characteristic morphologies, we highlight failures in some assumptions that are commonly applied when generating model parameters. Finally, by simulating exciton dynamics on a mapped Frenekel exciton model, we demonstrate the ability to quantify the effect of material morphology on the dynamic properties of excitons.