Orientation factors in three-centre energy pooling

At high levels of optical illumination, multichromophore arrays can exhibit a novel form of resonance energy transfer involving the coupling of two donors and one acceptor chromophore. This three-centre energy pooling is the subject of an investigation into its dependence on the mutual positions and orientations of the participating chromophores. Employing results obtained through quantum electrodynamical calculation, comparisons are made between pairwise resonance energy transfer and the novel three-body analogue, with counterparts to the conventional orientation factor identified. The interplay of such factors is analysed in the context of molecular architectures based on linear configurations. The relative dominance of cooperative and accretive mechanisms for energy pooling is addressed and the relative alignments and magnitudes of the donor and acceptor transition moments and polarisabilities are shown to have a profound effect on achievable pooling efficiency.