The J- and H-bands of dye aggregate spectra: Analysis of the coherent exciton scattering (CES) approximation

The validity of the CES approximation is investigated by comparison with direct diagonalisation of a model vibronic Hamiltonian of N identical monomers interacting electronically. Even for quite short aggregates (N greater than or similar to 6) the CES approximation is shown to give results in agreement with direct diagonalisation, for all coupling strengths, except that of intermediate Positive Coupling (the H-band region). However, previously excellent agreement of CES calculations and measured spectra in the H-band region was obtained [A. Eisfeld, J.S. Briggs, Chem. Phys. 324 (2006) 376]. This is shown to arise from use of the measured monomer spectrum which includes implicitly dissipative effects not present in the model calculation. (C) 2008 Elsevier B.V. All rights reserved.