Impact of Local and Nonlocal Vibronic Coupling on the Absorption and Emission Spectra of J- and H-Dimers.

The impact of exciton-vibrational (EV) coupling involving low-energy ("slow") intermolecular vibrations and higher-energy ("fast") intramolecular vibrations on the absorption and emission spectra of H- and J-dimers is studied theoretically for a pair of chromophores with excitonic coupling dominated by transition dipole-dipole coupling, JC. Exact quantum-mechanical solutions based on a Frenkel-Holstein-Peierls Hamiltonian reveal a fascinating interplay between the two coupling sources in determining the spectral line widths, Stoke shifts and radiative decay rates. It is shown that the ratio rules derived from the vibronic progression of the fast mode in molecular dimers remain valid under the influence of slow-mode EV coupling under most conditions. However, a highly unusual aggregate behavior occurs when the product of local and nonlocal couplings, |gLgNL|, exceeds 2ℏωs|JC|, where ℏωs is the energy of the slow mode. In this regime and when gL and gNL are in-phase, an H-dimer (JC > 0) becomes strongly emissive and can even be super-radiant, while a J-dimer (JC < 0) with out-of-phase gL and gNL values becomes subradiant. Such behaviors are in marked contrast to the predictions of Kasha theory and demonstrate the richness of the photophysical behavior resulting from EV coupling involving inter- and intramolecular vibrations.