The Influence of Geometry on the Vibronic Spectra of Quantum Aggregates

Abstract: A study is presented of the localisation of excitonic states on extended molecular aggregates composed of identical monomers arising, not from disorder due to statistical energy shifts of the monomers, induced by environmental interactions (Anderson localisation), but rather simply due to changes in the orientation and geometrical arrangement of the transition dipoles. It is shown further that such small changes nevertheless can have a drastic effect on the shape of the vibronic spectrum of the aggregate. The vibronic spectra are calculated using the "coherent exciton scattering" (CES) approximation whose derivation we generalise to be applicable to aggregates of arbitrary size and geometry.