Emission rate, vibronic entanglement, and coherence in aggregates of conjugated polymers

Here we have studied a dimer model of conjugated polymer aggregates based on the traditional J and H structures, with the extension in treating the electronic and vibrational degrees of freedom at par. We have considered various exchange symmetries corresponding to the parameters of the excited state Hamiltonian in assigning the symmetry of the vibronic states of the aggregate, going beyond the homodimer case. The emission rates are determined as a function of system parameters at low temperature for both types of aggregates. We have also determined the vibronic entanglement as a measure of the coupled electronic and vibrational motion as well as the exciton coherence number in the emitting state. As a function of interchain interaction strength, emission rate and entanglement grossly follow similar trends for the J-aggregate and opposite trends for the H-aggregate in totally symmetric as well as asymmetric cases. Variation of other system parameters, like electronic excitation energy and electron-vibration coupling parameter are also thoroughly investigated in governing these quantities. The role of symmetry of the wave function in governing the spectra and the exciton coherence are also analyzed thoroughly, which offers a way to realize the connection between such macroscopic and microscopic quantum features.