Exciton absorption spectra of optically excited linear molecular aggregates

Exciton absorption spectrum of optically excited linear molecular aggregate is theoretically investigated. The sum rules for the integral intensity of the absorption spectrum are derived. The dipole moments of the optical transitions from the one-exciton states to the two-exciton states are presented. The results obtained indicate an energy increase of the exciton transition after a single excitation of the aggregate. It accounts for the observed short-wavelength shift of the J-band of the pseudoisocyanine (PIC) J-aggregates after their optical excitation. The comparison of the experimental energy of the shift with its theoretical evaluation allows to estimate the number of monomers forming a typical PIC J-aggregate in the solutionN ?20–30.