Excitonic polarons in quasi-one-dimensional LH1 and LH2 bacteriochlorophyll a antenna aggregates from photosynthetic bacteria: A wavelength-dependent selective spectroscopy study

Spectral characteristics of the optically excited states in the ring-shaped quasi-one-dimensional aggregates comprising 18 and 32 tightly coupled bacteriochlorophyll a molecules have been investigated using selective spectroscopy methods and theoretical modelling of the data. Distinguished by the lowest electronic transition energies in the LH2 and LH1 antenna complexes these aggregates govern the functionally important ultrafast funneling of solar excitation energy in the photosynthetic membranes of purple bacteria. It was found by using a sophisticated differential fluorescence line narrowing method that exciton-phonon coupling in terms of the dimensionless Huang-Rhys factor is strong in these systems, justifying an excitonic polaron theoretical approach for the data analysis. Although we reached this qualitative conclusion already previously, in this work essential dependence of the exciton-phonon coupling strength and reorganization energy on excitation wavelength as well as on excitation light fluence has been established. We then show that these results corroborate with the properties of excitonic polarons in diagonally disordered ensembles of the aggregates. Furthermore, the weighted density of states of the phonon modes, which is an important characteristic of dynamical systems interacting with their surroundings, was derived. Its shape, being similar for all studied circular aggregates, deviates significantly from a reference profile describing local response of a protein to the Qy electronic transition in a single bacteriochlorophyll a molecule. Similarities of the data for regular and B800 deficient mutant LH2 complexes indicate that the B800 pigments have no direct influence on the electronic states of the B850 aggregate system. Consistent set of model parameters was determined, unambiguously implying that excitonic polarons, rather than bare excitons are proper lowest-energy optical excitations in the LH1 and LH2 antenna complexes.