Theory of the absorption and circular dichroism spectra of helical molecular aggregates

A theory of the electronic circular dichroism (CD) and optical rotatory dispersion (ORD) of infinite aggregates exhibiting cylindrical symmetry is presented in which, to the authors' knowledge, for the first time vibrational structure is included explicitly. It is shown that, with the coherent exciton scattering approximation in the Green function approach, the detailed vibrational structure of the aggregate absorption. CD and ORD bands can be calculated from a knowledge of the electronic coupling and the monomer absorption line shape alone. Detailed model calculations for a single helix are made and the results are used to expose the origin of different spectral features. A good reproduction of experimental J-aggregate spectra is obtained, using the same electronic interaction to fit both absorption and CD spectral line shapes. The theory allows some prediction of aggregate geometry to be made, but it is shown that an unambiguous geometrical assignment can only be made where experimental spectra for light of different propagation directions with respect to the cylinder axis are available. (c) 2007 American Institute of Physics.