Davydov Splitting Without a Davydov Pair and Highly Mobile Singlet Excitons in Perylene Red Microcrystals

Abstract

We investigate the excitonic properties of perylene red microcrystals, whose unit cell contain eight molecules, using both experimental and theoretical methods. Only two of the nominal eight Davydov transitions are experimentally observed, with an apparent splitting of 610 cm$^{-1}$ that is reasonably reproduced by a Frenkel-Holstein exciton model parametrized from density functional theory. A symmetry-based analysis of the eigenstates reveals that the two observed transitions do not belong to the same Davydov pair, so the splitting does not directly report on the Coulomb coupling within the unit cell. The complex mixture of local excitations produces a J-like band for the dominant transitions, favouring exciton transfer through increased spectral overlap. Consistent with this picture, time-correlated single-photon counting of the emission and ultrafast transient absorption spectroscopy show that the dynamics is dominated by highly mobile singlet Frenkel excitons. The exciton mobility extracted from experiment agrees very well with that obtained from Kinetic Monte Carlo simulations, supporting a picture of incoherent hopping transport.