Regimes of Exciton Transport in Molecular Crystals in the Presence of Dynamic Disorder

Thermal motions in molecular crystals cause substantial fluctuation of the excitonic coupling between neighboring molecules (dynamic disorder). The effect of such fluctuation on the exciton dynamics in two limiting cases is explored here, exemplified by the crystals of anthracene and a heteropentacene derivative. When the excitonic coupling is small in comparison with the electron-phonon coupling, the exciton diffusion is incoherent and the inclusion of excitonic coupling fluctuation does not alter the exciton physics but can improve the agreement between computed and experimental diffusion coefficients. For large excitonic couplings, when the transport becomes coherent, the thermal motions determine the diffusivity of the exciton, which can be several orders of magnitude larger than in the incoherent case. The coherent regime is less frequent but potentially of great technological importance.