The fundamental photophysics of conjugated oligomer herringbone aggregates

The photophysical properties of defect-free herringbone aggregates of π-conjugated oligomers are investigated theoretically using a two-particle basis set consisting of vibronic excitons and coupled vibronic–vibrational excitons. Incorporation of periodic boundary conditions allows the treatment of aggregates containing up to 1000 molecules. The vibrational distortion fields for the optically allowed excitons, including those responsible for the upper and lower Davydov components, are evaluated. The herringbone lattice supports both vibrationally dressed, heavy excitons as well as nearly free, light excitons. The former are responsible for the b-polarized absorption origin as well as two ac-polarized peaks slightly higher in energy. The strongly blueshifted main absorption peak is due to an exciton which travels with almost no nuclear distortion. The main absorption features are studied as a function of aggregate size and exciton bandwidth. The vibronic replicas in the aggregate emission spectrum are foun...