Excitation energy transfer between closely spaced multichromophoric systems Effects of band.pdfVIP

Excitation energy transfer between closely spaced multichromophoric systems: Effects of band mixing and intraband relaxation C. Didraga, V. A. Malyshev,∗ and J. Knoester† Institute for Theoretical Physics and Materials Science Centre, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands (Dated: February 3, 2008) 6 0 We theoretically analyze the excitation energy transfer between two closely spaced linear molecular 0 J-aggregates, whose excited states are Frenkel excitons. The aggregate with the higher (lower) 2 exciton band edge energy is considered as the donor (acceptor). The celebrated theory of F¨orster r resonance energy transfer (FRET), which relates the transfer rate to the overlap integral of optical p spectra, fails in this situation. We point out that in addition to the well-known fact that the point- A dipole approximation breaks down (enabling energy transfer between optically forbidden states), also the perturbative treatment of the electronic interactions between donor and acceptor system, 5 which underlies the F¨orster approach, in general loses its validity due to overlap of the exciton bands. We therefore propose a nonperturbative method, in which donor and acceptor bands are ] n mixed and the energy transfer is described in terms of a phonon-assisted energy relaxation process n between the two new (renormalized