  In a first-principles study based on density functional theory and many-body
perturbation theory, we address the interplay between intra- and intermolecular
interactions in a J-aggregate formed by push-pull organic dyes by investigating
its electronic and optical properties. We find that the most intense excitation
dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a
combination of intramolecular charge transfer, coming from the push-pull
character of the constituting dyes, and intermolecular charge transfer, due to
the dense molecular packing. We also show the presence of a pure intermolecular
charge-transfer excitation within the J-band, which is expected to play a
relevant role in the emission properties of the J-aggregate. Our results shed
light on the microscopic character of optical excitations of J-aggregates and
offer new perspectives to further understand the nature of collective
excitations in organic semiconductors.
